CN104302791B

CN104302791B - Method for processing red mud

Info

Publication number: CN104302791B
Application number: CN201380010871.5A
Authority: CN
Inventors: 理查德·鲍德劳尔特; 约耳·弗尔尼尔; 丹尼斯·普里茂; 玛丽-马克西姆·拉伯勒科库伊-吉尔伯特
Original assignee: Orbite Aluminae Inc
Current assignee: Orbite Technologies Inc
Priority date: 2012-01-10
Filing date: 2013-01-10
Publication date: 2017-03-15
Anticipated expiration: 2033-01-10
Also published as: CA2875776A1; CA2857574C; AU2013202318B2; EP2802675A4; CN104302791A; BR112014016732A8; US9023301B2; US9556500B2; RU2016104423A; WO2013104059A1; EP2802675A1; RU2579843C2; CA2857574A1; BR112014016732A2; AU2016200411A1; US20150275330A1; JP6025868B2; RU2014131946A; EP2802675B1; AU2013202318A1

Abstract

Provide the method for processing red mud.For example, the method can be included with HCl extraction red muds to obtain lixiviating solution and solid comprising the first metal (such as aluminum) ion, and the solid is separated with the lixiviating solution.Some other metals (Fe, Ni, Co, Mg, rare earth element, rare metal etc.) can be extracted from lixiviating solution.Can be from solids extract other components multiple, such as TiO₂、SiO₂Deng.

Description

Method for processing red mud

Cross reference to related applications

This application claims in the US 61/584,993 for submitting to of on January 10th, 2012, the US submitted to for 26th in September in 2012 61/706,074, and the priority of the US 61/713,719 submitted on October 15th, 2012.These documents will by quoting Entire contents are expressly incorporated herein.

Technical field

It relates to the improvement to processing industrial waste method field.For example, which relates to the method for processing red mud. For example, these methods effectively can extract various materials such as aluminium oxide and various metals and its oxide, dioxy from red mud SiClx, rare earth element, rare metal etc..

Open background

Red mud is the solid waste products produced during production aluminium oxide.For example, red mud is being given birth to for aluminium oxide In the Bayer process of product produce, the Bayer process be in order to Hall-H é roult methods electrolytic aluminium provide as raw material aluminium oxide Refine bauxite key industry means.The red mud of one to twice more than general factory's producing ratio aluminium oxide.This ratio depends on Type in bauxite or Ore used in refining process.

Generally, red mud includes solid and carries the mixture of the impurity of metal-oxide, and it is most important to assume aluminum industry One of process problem.Redness can be caused by (such as) oxidized ferrum present in which.Red mud cannot be disposed easily.? In the major part country of production red mud, which is pumped to holding pond (holding pond).Thus red mud becomes problem, because which accounts for With land area, even if when dried, building can neither be used for and cannot be used for cultivating.Red mud is (for example) overbasic. For example, pH may range from 10 to 13.Have been developed for several method and alkaline pH is reduced to acceptable level, so as to drop The low impact to environment.Some researchs have been completed, and the mode that mud is used for other application is suitable to so as to find, but drying should Mud needs big energy (for the latent heat of water evaporation), and if must use Fossil fuel in drying process, then may be used Show as high cost.

Global red mud amount constantly increases.Only in 2010,80,000,000 tons of aluminium oxide in world wide, is produced, produced super Cross 1.2 hundred million tons of red muds.According to estimates, in world wide red mud storage actually well beyond 2,500,000,000 tons.This numeral only meeting Constantly increase, because the increase in demand to aluminum drives the demand to aluminium oxide, and transfer for bauxite, it means that increase Generation added with malicious red mud residue.

Thus the confession substitution method for processing red mud is needed.

Disclosure

According on one side, there is provided the method for processing red mud, the method include：

With HCl extraction red muds to obtain comprising aluminum ions lixiviating solution and solid, and by the solid and the lixiviating solution Separate；

Make the lixiviating solution react with HCl to obtain liquid and include AlCl₃The aluminum ions precipitate of form, and this is sunk Starch is separated with the liquid；And

Effectively by AlCl₃Change into Al₂O₃Under conditions of heat the precipitate.

According on the other hand, there is provided the method for processing red mud, the method include：

Effectively by AlCl₃Change into Al₂O₃Under conditions of heat the precipitate, and the gaseous state produced by reclaiming HCl.

Effectively by AlCl₃Change into Al₂O₃Under conditions of heat the precipitate, and the gaseous state HCl produced by reclaiming.

According on the other hand, there is provided the method for preparing aluminium oxide and/or other products, the method include：

According on one side, there is provided the method for preparing aluminum, the method include：

Make the lixiviating solution react with HCl to obtain liquid and include AlCl₃The aluminum ions precipitate of form, and this is sunk Starch is separated with the liquid；

Effectively by AlCl₃Change into Al₂O₃Under conditions of heat the precipitate；And

Effectively by Al₂O₃The Al is processed under conditions of changing into aluminum₂O₃.

According on the other hand, there is provided the method for preparing aluminum, the method include：

With HCl extraction red muds to obtain comprising aluminum ions lixiviating solution and solid, and the solid and the lixiviating solution point From；

Effectively by AlCl₃Change into Al₂O₃Under conditions of heat the precipitate, and the gaseous state HCl produced by reclaiming； And

According on the other hand, there is provided the method for processing red mud, which includes：

Red mud is carried to obtain lixiviating solution and solid residue with acidleach, and the lixiviating solution is divided with the solid residue From；

By make the lixiviating solution and alkali reaction and under the pH more than 10 basic selective precipitation iron ion and from the leaching Extract removes the iron ion of precipitation at least in part, so as to go iron ions at least in part from the lixiviating solution, is derived from wrapping Contain Al³⁺The rich Al compositionss of ion；

Optionally purification Al³⁺Ion；And

Optionally by the Al³⁺Ion conversion is aluminium oxide.

According on the other hand, there is provided the method for preparing aluminium oxide and other optional products, the method include：

With material of the HCl extractions containing aluminum to obtain comprising aluminum ions lixiviating solution and solid, and by the solid and it is somebody's turn to do Lixiviating solution is separated；

By making produced gaseous state HCl contact with water come recirculation gaseous state HCl obtaining concentration higher than HCl azeotropic mixtures The compositionss of concentration (20.2wt%), and by the material reaction containing aluminum of said composition and additional amount extracting to which.

It is for about 18wt% to obtain concentration to be contacted with water come gaseous state HCl described in recirculation by the gaseous state HCl for making produced Compositionss to about 45wt% or about 25wt% to about 45wt%, and the material reaction containing aluminum by said composition and additional amount To extract to which.

It is for about 18wt% by making produced gaseous state HCl contact with water come recirculation such as gaseous state HCl to obtain concentration Compositionss to about 45wt% or about 25wt% to about 45wt%, and said composition is used for material of the extraction containing aluminum.

With material of the HCl extractions containing aluminum to obtain comprising aluminum ions lixiviating solution and solid, and from the solid and it is somebody's turn to do Lixiviating solution is separated；

Contacted with water come recirculation gaseous state HCl, so as to AlCl by the gaseous state HCl produced by making₃·6H₂O forms are sunk Shallow lake aluminium ion.

Effectively by AlCl₃Change into Al₂O₃Under conditions of heat the precipitate, and the gas produced by optionally reclaiming State HCl.

According on one side, there is provided the method for preparing aluminum and other optional products, the method include：

By Al₂O₃It is converted into aluminum.

According on the other hand, there is provided the method for preparing aluminum and other optional products, the method include：

Make the lixiviating solution react with HCl to obtain liquid and include AlCl₃The aluminum ions precipitate of form, and should Precipitate is separated with the liquid；

Effectively by AlCl₃Change into Al₂O₃Under conditions of heat the precipitate, and the gas produced by optionally reclaiming State HCl；And

By the Al₂O₃It is converted into aluminum.

According on the other hand, there is provided the method for preparing aluminum, which includes：

Obtain the aluminium oxide of method production defined in the disclosure；And

The aluminium oxide is processed under conditions of aluminium oxide to be changed into aluminum effectively.

With HCl red muds of the extraction comprising the first metal to obtain the lixiviating solution and solid of the ion comprising the first metal, And the solid is separated with the lixiviating solution；

Make the lixiviating solution the muriatic precipitate to obtain liquid and comprising the first metal be reacted with HCl, and which will The precipitate is separated with the liquid；And

The precipitate is heated under conditions of the oxide that the chloride of the first metal is effectively changed into the first metal.

According to another example, there is provided the method for preparing titanium oxide, the method include：

Red mud is extracted to obtain the first lixiviating solution and solid comprising the ion from least one metal with HCl, and And the solid is separated with first lixiviating solution；

From the ion that first lixiviating solution is at least substantially separate at least one metal；

The solid is extracted with HCl optionally in the presence of chloride to obtain the second lixiviating solution comprising titanium chloride；Or Person makes the solid and Cl₂To obtain liquid portion and solid portion comprising titanium chloride and solid from this with carbon source reaction Body portion is separated with the liquid portion；And

The titanium chloride is converted into titanium oxide.

The solid is extracted with HCl optionally in the presence of chloride to obtain the second lixiviating solution comprising titanium chloride；And And

The titanium chloride is converted into titanium oxide.

According to another example, there is provided the method for preparing titanium chloride, the method include：

From the ion that the lixiviating solution is at least substantially separate at least one metal；And

The solid is extracted with HCl optionally in the presence of chloride to obtain the second lixiviating solution comprising titanium chloride.

Red mud is extracted to obtain the first lixiviating solution and solid comprising the ion from least one metal with HCl, and And the solid is separated with the lixiviating solution；

From the ion that first lixiviating solution is at least substantially separate at least one metal；And

Make the solid and Cl₂With carbon source reaction to obtain liquid portion and solid portion comprising titanium chloride, and The liquid portion is separated with the solid portion.

It was found that disclosed method can be used for processing for example various Ores of various parent materials.It moreover has been found that except effective Outside such parent material is processed, industrial waste such as red mud can also be processed by such method.In fact it has been found that the disclosure Method effectively provide solution for red mud problem：These methods allow effectively to process red mud, and return from red mud Receive various valuable products.These methods be simple and effective, and can in an environment-friendlymanner manner low cost implement.

Brief description

The following drawings only assumes each embodiment of the disclosure by way of example：

Fig. 1 illustrates the block diagram for preparing the example of the method for aluminium oxide and various other products of the disclosure；

Fig. 2 is the extraction curve of Al and Fe, and wherein in the method for present application example, extraction ratio is expressed as extraction time Function；

Fig. 3 illustrates the block diagram for preparing another example of the method for aluminium oxide and various other products of the disclosure；

Fig. 4 is the schematic diagram of the example of the method for purifying/concentrating HCl of the disclosure；

Fig. 5 is the schematic diagram of the example of the method for purifying/concentrating HCl of the disclosure；

Fig. 6 illustrates another block diagram for preparing the example of the method for aluminium oxide and various other products of the disclosure；

Fig. 7 illustrates another block diagram for preparing the example of the method for aluminium oxide and various other products of the disclosure；

Fig. 8 illustrates another block diagram for preparing the example of the method for various products of the disclosure；

Fig. 9 illustrates another block diagram for preparing the example of the method for titanium chloride and/or titanium oxide of the disclosure；

Figure 10 A and Figure 10 B illustrate the another block diagram of the example of disclosed method；And

Figure 11 A and Figure 11 B illustrate another block diagram of the example of disclosed method.

Each embodiment is described in detail

Following non-limiting examples further illustrate the technology described in the disclosure.

Material containing aluminum can be selected from for example by Ore (such as aluminium silicate mineral, clay, argillaceous slate, the rosy clouds containing aluminum Stone, mud stone, beryl (beryl), cryolite, garnet, spinelle, bauxite, Kaolin or its mixture can make With).Containing aluminum material can also be reclaim industry containing aluminum material, such as slag (slag), red mud or flying dust.

Statement " red mud " used herein refer to for example production aluminium oxide during produced by industrial waste product.Example Such as, such waste products can include silicon dioxide, aluminum, ferrum, calcium and optional titanium.Which can include a collection of minor component, Na, K, Cr, V, Ni, Co, Ba, Cu, Mn, Mg, Pb and/or Zn etc..For example, red mud can include about 15wt% to 80wt% Fe₂O₃, the Al of about 1wt% to about 35wt%₂O₃, the SiO of about 1wt% to about 65wt%₂, about 1wt% is to about 20wt%'s Na₂The CaO of O, about 1wt% to about 20wt%, and about 0wt% to the TiO of about 35wt%₂.According to another example, red mud can To include the Fe of about 30wt% to 65wt%₂O₃, the Al of about 10wt% to about 20wt%₂O₃, about 3wt% is to about 50wt%'s SiO₂, the Na of about 2wt% to about 10wt%₂The CaO of O, about 2wt% to about 8wt%, and about 0wt% is to about 25wt%'s TiO₂.It will be understood to those of skill in the art that the composition of red mud can be according to the bauxite source used in Bayer process not With.

Statement " flying dust " used herein refers to produced industrial waste product in such as combustion process.For example, this Class waste product can include the various composition of such as silicon dioxide, oxygen, aluminum, ferrum, calcium.For example, flying dust can include silicon dioxide (SiO₂) and aluminium oxide (Al₂O₃).For example, flying dust can also include calcium oxide (CaO) and/or ferrum oxide (Fe₂O₃).For example, fly Ash can include the fine grained risen together with flue gas.For example, flying dust can be produced during coal combustion.For example, fly Ash can also include at least one selected from arsenic, beryllium, boron, cadmium, chromium, chromium VI, cobalt, lead, manganese, hydrargyrum, molybdenum, selenium, strontium, thallium and/or vanadium Element.For example, flying dust can also include rare earth element and rare metal.For example, flying dust can be considered the material containing aluminum.

Statement " rare earth element " used herein (being also been described as " REE ") refer to be selected from scandium, yttrium, lanthanum, cerium, The rare element of praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutecium.Statement " rare gold used herein Category " refers to the rare metal for being selected from indium, zirconium, lithium and gallium.These rare earth elements and rare metal can be various forms, all Such as element form (or metallic forms), in the form of chloride, oxide, hydroxide etc..The statement used by the disclosure The synonym of " rare earth " as " rare earth element and rare metal " as described above.

Statement " at least one iron chloride " used herein refers to FeCl₂、FeCl₃Or its mixture.

Term as used herein " bloodstone " is referred to₂O₃、γ-Fe₂O₃, β-FeO.OH or its mix The compound of thing.

Statement " iron ion " used herein is referred to for example includes at least one of Fe ions selected from be possible to form The ion of the iron ion of type.For example, the iron ion of at least one type can be Fe²⁺、Fe³⁺Or its mixture.

Statement " aluminium ion " used herein is referred to for example includes at least one of Al ions selected from be possible to form The aluminum ions ion of type.For example, the aluminium ion of at least one type can be Al³⁺.

Statement " at least one aluminium ion " used herein is referred to and is selected from the Al ions of be possible to form extremely Few a type of aluminium ion.For example, at least one aluminium ion can be Al³⁺.

Statement " at least one iron ion " used herein is referred to and is selected from the Fe ions of be possible to form extremely Few a type of iron ion.For example, at least one iron ion can be Fe²⁺、Fe³⁺Or its mixture.

Statement " iron ion of at least one precipitation " used herein refers to the institute for being selected from precipitating in solid form It is possible to the iron ion of at least one type of the Fe ions of form.For example, at least one ferrum present in such precipitate Ion can be Fe²⁺、Fe³⁺Or its mixture.

Degree term used herein such as " about " and " approximate " mean the legitimate skew amount of modified term, so that Final result is not changed significantly.The degree term is understood to include at least ± the 5% or at least ± 10% of modified term Deviation, as long as this deviation will not make the implication of its word that is modified invalid.

Term as used herein " ALP " refers to sour extraction equipment (Acid Leaching Plant).

Statement " titanium chloride " used herein is referred to and is selected from TiCl₂、TiCl₃And TiCl₄And its change of mixture Compound.For example, which refers to TiCl₄.

For example, the material can be extracted using HCl, and concentration for about 10wt% to about 50wt%, the about 15wt% of the HCl are extremely About 45wt%, about 18wt% to about 45wt%, about 18wt% to about 32wt%, about 20wt% to about 45wt%, about 25wt% extremely About 45wt%, about 26wt% to about 42wt%, about 28wt% to about 40wt%, about 30wt% to about 38wt% or 25wt% extremely 36wt%.It is, for example possible to use the HCl of about 18wt% or about 32wt%.

For example, the material can be extracted with HCl, the concentration of the HCl be for about 1M to about 12M, about 2M to about 10M, about 3M extremely About 9M, about 4M are to about 8M, to about 5M about 7M or about 6M.

Extraction can also dry high concentrated acid (for example, 85%, 90% or 95%) by add gas phase in aqueous solution Come carry out.Or, extraction can also be by using weak acid solution (for example<3wt%) come carry out.

For example, extraction can be for about the HCl of 18wt% to about 32wt% by concentration used in first reactor, then Carried out by the HCl of concentration used in second reactor for about 90% to about 95% (gaseous state).

For example, leaching can be for about the HCl of 18wt% to about 32wt% by concentration used in first reactor, then It is for about the HCl of 90% to about 95% (gaseous state) by concentration used in second reactor；And pass through in the 3rd reactor Concentration is for about the HCl of 90% to about 95% (gaseous state) carrying out.

For example, extraction can be carried out under inert gas atmosphere (such as argon or nitrogen).

For example, extraction can be in NH₃Carry out under atmosphere.

For example, the material can about 125 DEG C to about 225 DEG C, about 140 DEG C to about 165 DEG C, about 145 DEG C to about 160 DEG C, About 150 DEG C to about 200 DEG C, about 150 DEG C to about 190 DEG C, about 160 DEG C to about 190 DEG C, about 185 DEG C to about 190 DEG C, about 160 DEG C extremely Extract at a temperature of about 180 DEG C, about 160 DEG C to about 175 DEG C or about 165 DEG C to 170 DEG C.

For example, the material can be in about 4barg to about 10barg, about 4barg to about 8barg or about 5barg to about Extract under the pressure of 6barg.

For example, the material can be in about 50psig to about 150psig, about 60psig to about 100psig or about 70psig extremely Extract under the pressure of about 80psig.

For example, extraction can be for about the HCl of 18wt% to about 32wt% by concentration used in first reactor, then Carried out by the HCl of concentration used in second reactor for about 90% to about 95% or 95% to 100% (gaseous state).

For example, extraction can be in NH₃Carry out under atmosphere.

For example, the first extraction can be carried out at ambient pressure, and then can reduce pressure carries out at least one other extraction (for example 1,2 or 3 follow-up leach step).

For example, before methods described is additionally may included in extraction red mud, pre- extraction removal optionally includes in the red mud Fluorine.

Before extraction, material for example can be processed by ball mill.For example, red mud can be reduced to 80%, 85% or 90% is sieved by 63 μm.

For example, extraction can be continuous extraction or semi-continuous.

For example, disclosed method can be continuous or semi-continuous.

For example, the method can also include contacting with water come gaseous state HCl described in recirculation by making produced gaseous state HCl With acquisition concentration for about 18wt% to about 45wt%, about 26wt% to about 42wt%, about 25wt% to about 45wt%, about 28wt% To about 40wt%, about 30wt% to about 38wt%, about 18% to about 36% or the compositionss of %.

For example, the process can also include contacting with water come gaseous state HCl described in recirculation by making produced gaseous state HCl To obtain the compositionss that concentration is for about 18wt% to about 45wt% or about 25wt% to about 45wt%, and said composition is used for Extraction material.

For example, liquid can include iron chloride.Iron chloride can include FeCl₂、FeCl₃And its in mixture extremely Few one kind.

For example, liquid can have the iron chloride concentration of at least 30wt%；Then can be at about 155 DEG C to about 350 DEG C At a temperature of hydrolyze.

For example, it is at least concentrated solution of 30wt% that the liquid can be concentrated into iron chloride concentration；Then iron chloride Can hydrolyze at a temperature of about 155 DEG C to about 350 DEG C, while ferric chloride concn is maintained at least level of 65wt%, with The compositionss of the bloodstone comprising liquid and precipitation are generated, and reclaims bloodstone.

For example, the non-hydrolysable composition of bloodstone can be concentrated back in the closed circuit based on selective extraction about The concentration of 0.125wt% to about 52wt%.

For example, it is at least concentrated solution of 30wt% that the liquid can be concentrated at least one iron chloride concentration；Then exist Hydrolyze at a temperature of about 155 DEG C to about 350 DEG C.

For example, it is at least concentrated solution of 30wt% that the liquid can be concentrated at least one iron chloride concentration；Then will At least one iron chloride is hydrolyzed at a temperature of about 155 DEG C to about 350 DEG C, while ferric chloride concn is maintained at least The level of 65wt%, to generate the compositionss of the bloodstone comprising liquid and precipitation, and reclaims bloodstone.

For example, it is at least concentrated solution of 30wt% that the liquid can be concentrated at least one iron chloride concentration；Then will At least one iron chloride is hydrolyzed at a temperature of about 155 DEG C to about 350 DEG C, while ferric chloride concn is maintained at least The level of 65wt%, to generate the compositionss of the bloodstone comprising liquid and precipitation；Reclaim bloodstone；And return from the liquid Receive rare earth element and/or rare metal.

For example, at least one iron chloride can be at about 150 DEG C to about 175 DEG C, 155 DEG C to about 170 DEG C or 165 DEG C Hydrolyze at a temperature of about 170 DEG C.

For example, it is at least concentrated solution of 30wt% that the liquid can be concentrated to iron chloride concentration；Then can be by the ferrum chlorine Compound is hydrolyzed at a temperature of about 155 DEG C to about 350 DEG C, while ferric chloride concn is maintained at least level of 65wt%, with Generate the compositionss of the bloodstone comprising liquid and precipitation；Reclaim bloodstone；And from the liquids recovery rare earth element and/or Rare metal.

For example, after the method is additionally may included in recovering rare earth element and/or rare metal, liquid is made to react with HCl To cause MgCl₂Precipitation, and reclaimed.

For example, the method can also be included MgCl₂It is sintered into MgO.

For example, the method can also include MgCl₂MgO is sintered into, and is connect with water by the gaseous state HCl produced by making Touch and carry out gaseous state HCl described in recirculation to obtain the compositionss that concentration is for about 25wt% to about 45wt% or about 18 to about 45wt%, And it is used for extracting red mud by said composition.

For example, after the method can be additionally included in recovering rare earth element and/or rare metal, liquid is made to react with HCl, and And basic selective precipitation Na₂SO₄.For example, Na₂SO₄Can be by making liquid and H₂SO₄React and precipitate.

For example, after the method can be additionally included in recovering rare earth element and/or rare metal, liquid is made to react with HCl, and And basic selective precipitation K₂SO₄.For example, K₂SO₄Can pass through to add H₂SO₄And precipitate.

For example, it is at least concentrated solution of 30wt% that the liquid can be concentrated to iron chloride concentration；Then iron chloride exists Hydrolyze at a temperature of about 155 DEG C to about 350 DEG C, while ferric chloride concn is maintained at least level of 65wt%, to generate bag Compositionss containing liquid and the bloodstone of precipitation；Reclaim bloodstone；And liquid is reacted with HCl.For example, such method may be used also To include making liquid and H₂SO₄Reaction is with basic selective precipitation Na₂SO₄.For example, the method can also include make liquid with H₂SO₄Reaction is with basic selective precipitation K₂SO₄.

For example, methods described can include make in methods described obtain drying indivedual salt (such as Na or K salt) with H₂SO₄Reaction, and HCl is reclaimed, while producing salable K₂SO₄And Na₂SO₄, and about 15wt% is reclaimed to about 90wt% Hydrochloric acid.

For example, the sodium chloride for producing in the process can experience with the chemical reaction of sulphuric acid with obtain sodium sulfate and Regeneration hydrochloric acid.Potassium chloride can be experienced with the chemical reaction of sulphuric acid obtaining potassium sulfate and regenerate hydrochloric acid.Sodium chloride and chlorination Potassium salt aqueous solution can alternatively as the small-sized chlor-alkali electrolysis pond of adjusted (adapted) charging.In latter event In, produce common alkali (NaOH and KOH) and bleach (NaOCl and KOCl).

For example, after the method is additionally may included in recovering rare earth element and/or rare metal, from liquids recovery NaCl, Make NaCl and H₂SO₄Reaction, and basic selective precipitation Na₂SO₄.

For example, the method is additionally may included in the downstream of rare earth element and/or rare metal recovery, from liquids recovery KCl, Make KCl and H₂SO₄Reaction, and basic selective precipitation K₂SO₄.

For example, the method is additionally may included in the downstream of recovering rare earth element and/or rare metal, from liquids recovery NaCl, is electrolysed to generate NaOH and NaOCl.

For example, the method is additionally may included in the downstream of recovering rare earth element and/or rare metal, from liquids recovery KCl, React KCl, be electrolysed to generate KOH and KOCl.

For example, it is at least concentrated solution of 30wt% that the liquid can be concentrated at least one iron chloride concentration；Then should At least one iron chloride is hydrolyzed at a temperature of about 155 DEG C to about 350 DEG C, while ferric chloride concn is maintained at least The level of 65wt%, to generate the compositionss of the bloodstone comprising liquid and precipitation, and reclaims bloodstone；And carry from liquid Take NaCl and/or KCl.

For example, the method can also include making NaCl and H₂SO₄Reaction is with basic selective precipitation Na₂SO₄.

For example, the method can also include making KCl and H₂SO₄Reaction is with basic selective precipitation K₂SO₄.

For example, the method can also be comprising carrying out the electrolysis of NaCl to generate NaOH and NaOCl.

For example, the method can also be comprising carrying out the electrolysis of KCl to generate KOH and KOCl.

For example, the method can include separating solid with lixiviating solution and washing the solid, be at least so as to obtain purity 95%th, at least 96%, at least 97%, at least 98%, at least 99%, at least 99.5% or at least 99.9% silicon dioxide.

For example, the method can include making lixiviating solution react with gaseous state HCl, so as to obtaining liquid and including chloride shape The precipitate of the first metal of formula.

For example, the method can include the gaseous state HCl reactions for making lixiviating solution with drying, so as to obtaining liquid and including chlorine The precipitate of the first metal of compound form.

For example, precipitate A lCl₃Crystalline A lCl can be included₃·6H₂O.

For example, the HCl that the method can include lixiviating solution with make to reclaim in the process and concentration is at least 30% Reaction, so as to obtaining liquid and including aluminum ions precipitate, the precipitate passes through crystalline A lCl₃·6H₂O and formed.

For example, the first metal can be selected from aluminum, ferrum, zinc, copper, gold, silver, molybdenum, cobalt, magnesium, lithium, manganese, nickel, palladium, platinum, thorium, phosphorus, Uranium and titanium, and/or at least one rare earth element and/or at least one rare metal.

For example, liquid can include the second metal.

For example, the second metal can be selected from aluminum, ferrum, zinc, copper, gold, silver, molybdenum, cobalt, magnesium, lithium, manganese, nickel, palladium, platinum, thorium, phosphorus, Uranium and titanium, and/or at least one rare earth element and/or at least one rare metal.

For example, the second metal can be ferrum.

For example, the method can include separating precipitate with liquid, and heat the second metal with bimetallic by Chloride is converted into bimetallic oxide.

For example, the method can include：

Solid is separated with lixiviating solution；

With sour leached solids obtaining another kind of lixiviating solution；And

The 3rd metal is reclaimed from another kind of lixiviating solution.

For example, the 3rd metal can be selected from aluminum, ferrum, zinc, copper, gold, silver, molybdenum, cobalt, magnesium, lithium, manganese, nickel, palladium, platinum, thorium, phosphorus, Uranium and titanium, and/or at least one rare earth element and/or at least one rare metal.

For example, the 3rd metal can be titanium.

For example, the acid for extracting can be selected from HCl, HNO₃、H₂SO₄And its mixture.

For example, the acid can be HCl.

For example, the acid can be gaseous state HCl.

For example, the method can include by precipitating the 3rd metal and reclaim the 3rd metal from another kind of lixiviating solution.

For example, the 3rd metal can be precipitated by making which be reacted with HCl.

For example, the method can also include the 3rd metal of heating the chloride of the 3rd metal is converted into the 3rd metal Oxide.

For example, the first metal can be aluminum.

For example, the first metal can be magnesium.

For example, the first metal can be nickel.

For example, the second metal can be magnesium.

For example, the second metal can be nickel.

For example, the method can include making lixiviating solution react with gaseous state HCl, so as to obtaining liquid and including AlCl₃· 6H₂The aluminum ions precipitate of O forms.

For example, the method can include the gaseous state HCl reactions for making lixiviating solution with drying, so as to obtaining liquid and including AlCl₃·6H₂The aluminum ions precipitate of O forms.

For example, the method can include making lixiviating solution and reclaiming as pointed by the disclosure, regenerate and/or purification At least acid reaction of 30wt%, so that obtain liquid and comprising AlCl₃·6H₂The aluminum ions precipitate of O forms.

For example, the method can include making lixiviating solution react with gaseous state HCl, so as to obtaining liquid and including aluminum ions Precipitate, the precipitate pass through crystalline A lCl₃·6H₂O and formed.

For example, the method can include the gaseous state HCl reactions for making lixiviating solution with drying, so as to obtaining liquid and including aluminum The precipitate of ion, the precipitate pass through crystalline A lCl₃·6H₂O and formed.

For example, aluminium ion can be with AlCl₃(such as AlCl₃·6H₂O form) is precipitated in a crystallizer, for example, is passed through Add the HCl that concentration is for about 26wt% to about 32wt%.

For example, gaseous state HCl can have the HCl concentration of at least 85wt% or at least 90wt%.

For example, gaseous state HCl can have the HCl concentration of about 90wt% or about 90wt% to about 95wt%.

For example, in AlCl₃·6H₂In O crystallization processs, liquid can keep for about 25wt% to about 35wt% or about The HCl concentration of 30wt% to about 32wt%.

For example, crystallization can be carried out at a temperature of about 45 DEG C to about 65 DEG C or about 50 DEG C to about 60 DEG C.

For example, AlCl₃.6H₂The crystallization of O can be dissociated with reaching to set up in a crystallizer by adding the gaseous state HCl for concentrating The proprietary concentration of HCl is carrying out.The average product (results) obtained from crystal, such as hexahydrate crystal can be supplied in Calcining unit.AlCl₃Hydrolysis and conversion can occur low-down temperature (<200 DEG C) under.The crystal can pass through first Step, wherein decomposes and is followed by being calcined.Can be forged than hexahydrate crystal with consumption of energy with operation circulation fluid bed Burn commonly required energy little by 30%.If desired, produced aluminium oxide can be washed to remove unconverted salt.

For example, HCl can be obtained by produced gaseous state HCl.

For example, in disclosed method, the material containing aluminum of given batch or amount will be leached, and then will be converted Into AlCl₃, and now, AlCl₃Calcine as Al₂O₃During produce HCl will be used for extracting another given batch Or the material containing aluminum of amount.

For example, the method can include with least 180 DEG C, 230 DEG C, 250 DEG C, 300 DEG C, 350 DEG C, 400 DEG C, 450 DEG C, 500℃、550℃、600℃、650℃、700℃、750℃、800℃、850℃、900℃、925℃、930℃、1000℃、1100 DEG C, the temperature of 1200 DEG C or 1250 DEG C heat the precipitate, by AlCl₃Change into Al₂O₃.

For example, by AlCl₃Change into Al₂O₃AlCl can be included₃Calcining.

For example, calcining is to by AlCl₃Change into β-Al₂O₃It is effective.

For example, calcining is to by AlCl₃Change into α-Al₂O₃It is effective.

For example, by AlCl₃Change into Al₂O₃Can include being calcined by two benches circulating fluid bed reactor.

For example, by AlCl₃Change into Al₂O₃Can include that the two benches recirculating fluidized bed by including pre-heating system reacts Device is calcined.

For example, by AlCl₃Change into Al₂O₃E.g., from about 300 DEG C to about 600 DEG C, about 325 DEG C to about 550 can be included in DEG C, about 350 DEG C to about 500 DEG C, about 375 DEG C to about 450 DEG C, about 375 DEG C to about 425 DEG C or about 385 DEG C to about 400 DEG C low Calcined under temperature and/or under injection steam.

For example, by AlCl₃Change into Al₂O₃Can be included in for example, at least 180 DEG C, at least 250 DEG C, at least 300 DEG C, extremely Calcined in a low temperature of few 350 DEG C and/or under injection steam.

For example, by AlCl₃Change into Al₂O₃Can be included in a low temperature of e.g., less than 600 DEG C and/or spray under steam Calcined.

For example, by AlCl₃Change into Al₂O₃Can include as Combustion Source and single by using degassing by using coal Unit is being calcined.

For example, the method can be included by carrying out AlCl₃·6H₂O calcinings and by AlCl₃·6H₂O changes into Al₂O₃, should Calcining includes that steam sprays.

For example, steam (or water vapour) can in about 200psig to about 700psig, about 300psig to about 700psig, about 400psig to about 700psig, about 550psig are to about 650psig, about 575psig to about 625psig or about 590psig to about Spray under the pressure of 610psig.

For example, it is possible to spray steam (or water vapour) and plasma torch can be used for being fluidized.

For example, steam (or water vapour) can be overheated.

For example, steam (or water vapour) can be about 300 DEG C to about 400 DEG C of temperature.

For example, the acid from the waste gas produced during calcining subsequently can be processed by vapor phase purification method.

For example, by AlCl₃Change into Al₂O₃Can include being calcined with carbon monoxide (CO).

For example, by AlCl₃Change into Al₂O₃Can include being forged with refinery gas (Refinery Fuel Gas, RFG) Burn.

For example, calcining can pass through to spray water vapour or steam and/or by using selected from Fossil fuel, carbon monoxide, The Combustion Source of refinery gas, coal or chlorine-containing gas and/or solvent is carrying out.

For example, calcining can pass through to spray water vapour or steam and/or by using the burning selected from natural gas or propane Source is carrying out.

For example, calcining can be carried out by providing heat with electrical heating, gas heating, microwave heating.

For example, the method can be included with Al (OH)₃Form precipitate A l³⁺Ion.For example, with Al (OH)₃Form precipitate A l³⁺ Ion is about 7 to about 10；About 9 to about 10；About 9.2 to about 9.8；About 9.3 to about 9.7；About 9.5；7.5 to about 8.5；About 7.8 To about 8.2；Or about 8 pH under carry out.

For example, iron ion can be in the pH more than 11, the pH more than 12, the pH between 10 to 11, about 11.5 to about Precipitate under 12.5 pH, or the pH of about 11.8 to about 12.0.

For example, Al³⁺Ion is purified.

For example, the method can be included with AlCl₃Form precipitate A l³⁺Ion, so as to purification Al³⁺Ion.For example, precipitate AlCl₃Can pass through with AlCl₃·6H₂The form crystalline A lCl of O₃Come carry out.

For example, the method can be included AlCl₃Change into Al₂O₃, for example, by under inert gas atmosphere by AlCl₃ Change into Al₂O₃, or pass through in a nitrogen atmosphere by AlCl₃Change into Al₂O₃.

Can be by water washing be softened, to remove NaCl and/or KCl at least in part by obtained aluminium oxide.

For example, fluidized-bed reactor can include the metallic catalyst selected from metal chloride.

For example, fluidized-bed reactor can include metallic catalyst, and which is FeCl₃、FeCl₂Or its mixture.

For example, fluidized-bed reactor can include metallic catalyst, and which is FeCl₃.

For example, pre-heating system can include plasma torch.

For example, it is possible to steam is used as heating fluidizing agent.Heating can also be electric.

For example, plasma torch can be used for preheating the calcination reactor.

For example, plasma torch can be used for preheating the air for entering the calcination reactor.

For example, plasma torch can be used for generating the steam for spurting into calcination reactor.

For example, plasma torch can be effective for producing steam in a fluidized bed reactor as fluidizing agent.

For example, plasma torch can be used for preheated fluidification bed.

For example, calcining medium is for O₂(or oxidation) can be basic neutral.For example, calcining medium can be conducive to also Former (the CO concentration of e.g., from about 100ppm).

For example, calcining medium can be effectively prevented Cl₂Formation.

For example, the method is may include by carrying out AlCl₃·6H₂The calcining of O and by AlCl₃·6H₂O changes into Al₂O₃, example Such as, the calcining is provided by the burning comprising following admixture of gas：

CH₄：0 to about 1vol%；

C₂H₆：0 to about 2vol%；

C₃H₈：0 to about 2vol%；

C₄H₁₀：0 to about 1vol%；

N₂：0 to about 0.5vol%；

H₂：About 0.25 to about 15.1vol%；

CO：About 70 to about 82.5vol%；With

CO₂：About 1.0 about 3.5vol%

Such mixture can efficiently reduce 15.3% to 16.3% exhaust gas volume；Therefore the reality based on recirculating fluidized bed Border operates, it was demonstrated that 15.3% to 16.3% capacity increment.Therefore, for identical stream, 0.65*16.3%=this represent 10.6% operation expenditure (Opex).

For example, in fluid bed air and natural gas ratio (Nm³/ h compares Nm³/ h) 9.5 are can be about to about 10.

For example, in fluid bed air and CO gases ratio (Nm³/ h compares Nm³/ h) 2 are can be about to about 3.

For example, the admixture of gas can be substantially absent from O₂.

For example, before the method can be included in material of the extraction containing aluminum, pre- extraction is removed in the material containing aluminum optionally Comprising.

For example, the method can include extracting the material for containing aluminum to obtain comprising aluminum ions lixiviating solution and consolidate with HCl Body, the solid is separated with the lixiviating solution；And the solid is further processed with by the SiO for wherein including₂With TiO₂Separate.

For example, the method can include extracting the material for containing aluminum to obtain comprising aluminum ions lixiviating solution and consolidate with HCl Body, the solid is separated with the lixiviating solution；And further process the solid to separate the Si for wherein including with Ti.

For example, the method can include extracting the material for containing aluminum to obtain comprising aluminum ions lixiviating solution and consolidate with HCl Body, the solid is separated with the lixiviating solution；And further the solid is processed with HCl separating the Si for wherein including with Ti.

For example, the method can be included with HCl extraction red muds to obtain comprising aluminum ions lixiviating solution and solid, should Solid is separated with the lixiviating solution；And further (alkali metal chloride and alkaline-earth metal is selected from HCl in the presence of chloride Chloride) process the solid to separate the Si for wherein including with Ti.

For example, the solid can be with HCl and chloride treatment obtaining the liquid portion comprising Ti and the solid comprising Si Part, and wherein the liquid portion is separated with the solid portion.

For example, the solid can be with HCl and chloride treatment obtaining comprising TiCl₄Liquid portion.

For example, the method can also include TiCl₄Change into TiO₂.

For example, TiCl₄Titanium Dioxide can be formed by the solvent extraction of the 3rd liquid distillate and subsequently by solvent extraction And change into TiO₂.

For example, TiCl₄Can with water and/or alkali reaction so that TiO₂Precipitation.

For example, TiCl₄TiO can be converted into by pyrohydrolysises₂, thus produce HCl.

For example, TiCl₄TiO can be converted into by pyrohydrolysises₂, thus produce the HCl being recycled.

For example, solid can include TiO₂And SiO₂, and solid can use Cl₂With carbon process with obtain liquid portion and Solid portion, and the wherein solid portion is separated from one another with the liquid portion.

For example, liquid portion can include TiCl₂And/or TiCl₄.

For example, liquid portion can include TiCl₄.

For example, the method can also include heating TiCl₄To convert it into TiO₂.

For example, obtained TiO₂Can by plasma torch purification.

For example, the method can include extracting the material for containing aluminum to obtain comprising aluminum ions lixiviating solution and consolidate with HCl Body, the solid is separated with the lixiviating solution；And further with concentration less than 20wt% HCl less than at a temperature of 85 DEG C, The solid is processed in the presence of chloride, so as to separate the Si for wherein including with Ti.

For example, chloride can be selected from alkali metal chloride and alkaline earth metal chloride.

For example, chloride can be MgCl₂Or CaCl₂.

After extraction, titanium ion is in liquid phase in the form of titanium chloride, and Si keeps solid.Therefore, Si can be with letter Singly separated with Ti by solid/liquid separation.Then, titanium chloride can be converted into TiO₂.It should be noted that titanium oxychloride It also is present in the lixiviating solution.

The various methods from lixiviating solution recovery Pd are discussed in CA2513309, and entire contents are by quoting entirety simultaneously Enter text.

For example, separation method such as solvent extraction, precipitation or ion exchange can be used for removing impurity, and various impurity are such as Ferrum, chromium and vanadium, are followed by the recovery of titanium.Some in these technology discuss that in US6500396 (entire contents are by quoting It is integrally incorporated herein).

For example, for purification titanium ion, lixiviating solution can use organic phase processor.The organic faciess can be selected, so as to give Fixed ion optionally can be extracted into organic faciess, and titanium ion is stayed in aqueous.Accordingly it is also possible to obtain high-purity The given metal oxide.

The example of organic faciess is aliquat, amine (primary, secondary or tertiary), phosphoric acid and phosphinic acid and its ester and oxide, example Such as tricresyl phosphate-N-butyl, two -2- ethylhexyl phosphoric acids and phosphine oxide.Organic faciess can be stripped ferrum value, and reclaim.Can select Such organic faciess are selected, so that titanium chloride can be solvable in organic faciess.For example, organic faciess are selected, so that this is organic (separation of the boiling point for example between organic faciess and titanium chloride) can be separated with titanium chloride by fractional distillation.

For example, titanium chloride can be processed with water or alkali (such as magnesium oxide), or is lifted by the temperature by solution To 85-110 DEG C, to realize the precipitation of Titanium Dioxide.

Obtained titanium chloride product can also be calcined in high-temperature hydrolysis device or in plasma torch Middle process, to convert it into TiO₂.

For example, by AlCl₃Change into Al₂O₃Can include carries out one-step calcination.

For example, calcining can be carried out at different temperatures by steam.The temperature of the superheated steam of application can be about 350 DEG C to about 550 DEG C or about 350 DEG C to about 940 DEG C or about 350 DEG C to about 1200 DEG C.

For example, it is possible to the multistage evaporation step of the device that is hydrolyzed is being greatly lowered energy consumption.

For example, the method can effectively provide at least 93%, at least 94%, at least 95%, about 90% to about 95%, about 92% to about 95% or the Al of about 93% to about 95%₂O₃The response rate.

For example, the method can effectively provide at least 98%, at least 99%, about 98% to about 99.5%, or about 98.5% To about 99.5% Fe₂O₃The response rate.

For example, the method can effectively provide at least 96%, at least 97%, at least 98% or about 96% to about 98% The MgO response rate.

For example, the method can effectively provide the HCl response rate of at least 98%, at least 99% or about 98% to about 99.9%.

For example, it is for about 75% that the method can effectively provide the response rate by using the internal procedure in concentration inside loop To about 96.5% rare earth element chloride (REE-Cl) and rare metal chloride (RM-Cl).

For example, the method can effectively provide about 99.75% HCl recovery rate to non-hydrolysable composition.

For example, the material containing aluminum can be red mud.

For example, the material containing aluminum can be selected from industrial refractory material.

For example, the material containing aluminum is selected from aluminosilicate mineral.

For example, the method can be prevented effectively from generation red mud.

For example, obtained aluminium oxide and other products are substantially free of red mud.

For example, HCl can be recycled.For example, can should be concentration and/or purification in the HCl of circulation.

For example, the HCl of recovery for gaseous state HCl and can use H₂SO₄Process to reduce existing in gaseous state HCl The water yield.

For example, the HCl of recovery can be gaseous state HCl and can pass through packed column with H₂SO₄Counter current contacting, so as to drop The low water yield present in gaseous state HCl.

For example, gaseous state HCl passes through H₂SO₄Can be concentrated and/or purification.For example, gaseous state HCl can be by packed column, its In make itself and H₂SO₄Counter current contacting.For example, by doing so it is possible, the concentration of HCl can increase at least 50wt%, at least 60wt%, At least 70wt%, at least 75wt%, at least 80wt%, about 50wt% are to about 80wt%, about 55wt% to about 75wt% or about 60wt%.For example, the post can be filled with polymer such as polypropylene (PP) or propylene glycol ester terephthalate (PTT).

For example, gaseous state HCl can pass through CaCl₂Or LiCl and concentrate and/or purification.For example, gaseous state HCl can be by filling out Filled with CaCl₂Or the post of LiCl.By doing so it is possible, the water yield in HCl can be reduced.

For example, the concentration of gaseous state HCl from the value less than azeotropic point of before processing increase to process after higher than azeotropic point Value.

For example, once crystallization, alkali metal (mainly Na) can be processed to reclaim the hydrochloric acid (HCl) of high enrichment. The method selected for conversion can produce the value added product that commonly uses in chemical industry.For example, it is to produce from alkali (alkali) Bleach, can be to adjusted small-sized chlor-alkali electrolysis pond supply sodium chloride salt aqueous solution.Which can be such as two-step method, its In make saline experience high current, and use chlorine (Cl₂) and hydrogen (H₂) production alkali (NaOH).H can be made₂And Cl₂The conventional fire of experience The acid of flame, wherein high enrichment is produced with gas phase and is used directly for crystallization stage.

For example, the various products for being obtained by disclosed method such as aluminium oxide, bloodstone, titanium oxide, magnesium oxide, dilute Earth elements and rare earth metal etc. can also by plasma torch purification.For example, it is possible to which is individually spurted into etc. from Daughter torch is being further purified.

For example, the method can also be included aluminium oxide (Al₂O₃) it is converted into aluminum.Aluminium oxide is changed into aluminum can be such as Carried out by using Hall-H é roult methods.In various patents and patent applicationss such as US20100065435；US20020056650； US5876584；Such known method is referred in US6565733.Conversion can also be converted by other methods, Such as US7867373；US4265716；Aluminium oxide (is changed into aluminium sulfide, subsequently will by those methods described in US6565733 Aluminium sulfide is converted into aluminum).For example, aluminum can be produced at a temperature of less than 200 DEG C by using reducing environment and carbon.Aluminum also may be used To be produced by using potassium and anhydrous chlorine chloride reduction (Wohler methods).For example, wherein by Al₂O₃Changing into aluminum can be By by Al₂O₃Change into Al₂S₃, then by Al₂S₃Change into aluminum and carry out.

For example, the method can include making lixiviating solution react with gaseous state HCl to obtain liquid and include MgCl₂Precipitation Thing.

For example, the NaCl for being reclaimed from disclosed method can be with SO₂Reaction, so that produce HCl and Na₂SO₄.So Reaction be exothermic reaction, which can produce the steam that can be used to making turbine activity and finally generate electricity.

For example, solid can include TiO₂And SiO₂And solid can use Cl₂With carbon process, with obtain liquid portion and Solid portion, and wherein will be separated from one another to the solid portion and the liquid portion.

For example, at least one metal can include selected from such as aluminum, ferrum, zinc, copper, gold, silver, molybdenum, cobalt, magnesium, lithium, Manganese, nickel, palladium, platinum, thorium, phosphorus, uranium and titanium, and/or the first gold medal of at least one rare earth element and/or at least one rare metal Category.

For example, the first metal can be aluminum.

For example, the method can include making the first lixiviating solution react with gaseous state HCl to obtain liquid and include aluminum ions Precipitate, the precipitate pass through crystalline A lCl₃·6H₂O and formed.

For example, the method can include making the first lixiviating solution react with the gaseous state HCl for drying to obtain liquid and include aluminum The precipitate of ion, the precipitate pass through crystalline A lCl₃·6H₂O and formed.

For example, the first lixiviating solution can include Al ions and/or Fe ions.

For example, Al ions can substantially selectively with AlCl₃·6H₂The form of O is from the first extraction liquid precipitate.

For example, Fe ions can be by being translated into Fe via hydrolysis₂O₃And substantially selectively extract.

For example, solid can include TiO₂And SiO₂And solid can use Cl₂Process with carbon, to obtain including titanium chlorination The liquid portion and solid portion of thing, and wherein will be separated from one another to the solid portion and the liquid portion.

For example, including heating titanium chloride to convert it into TiO₂.

An example according to Fig. 1, the method can involve the steps of (reference markss in Fig. 1 correspond to Lower step)：

It is for about 50 μm to about 80 μm that 1- makes the material containing aluminum be decreased to mean diameter.

The material HCl treatment that 2- reduces and classifies, its allow to dissolve aluminum and other compositions at predetermined temperature and pressure Such as ferrum, magnesium and other metals including rare earth element and/or rare metal.Silicon dioxide and titanium (if existing in the feed) are protected Hold completely not molten.

Then 3- experiences separation, wash phase from the mother solution of leach step, is separated with the metal chloride from solution The silicon dioxide of purification.Then the Silicon stone of purification can be optionally subjected to one or two extra leaching stages (for example about At a temperature of 150 DEG C to about 160 DEG C) so that the purity of silicon dioxide increases above 99.9%.Include in silica TiO₂Can pass through HCl and MgCl₂Be used as lixivant compositionss and the extraction that carries out separating with silicon dioxide.

Then 4- is carried by the gaseous hydrogen chloride by spraying the gaseous hydrogen chloride of dry and high enrichment in a crystallizer The concentration of the spent acid (lixiviating solution) that height is obtained from step 1.This causes aluminum chloride hexahydrate (precipitate) crystallization and has minimum Other impurity.According to the concentration in this stage iron chloride, further crystallisation step can be needed.Then by the precipitate with Liquid is separated.For example, the particle diameter of crystal can be about 100 μm to about 500 μm, about 200 μm to about 400 μm or about 200 μm to about 300μm.Or, the particle diameter of crystal can be about 100 μm to about 200 μm, about 300 μm to about 400 μm or about 400 μm to 500 μ m.

The 5- aluminum chloride hexahydrates and then at high temperature calcining (for example, by rotary kiln, fluid bed etc.), to obtain oxygen Change aluminum form.Then the gaseous hydrogen chloride of high enrichment is reclaimed, and makes the highest that its excess is possibly realized as an aqueous solution Concentration, so as to used in sour leach step (recirculation).Acid can also be directly sent to sour purification phase with gas phase so that HCl is dense Degree increases to about 95wt% from about 30wt%.This can accomplish, for example, during drying stage.

6- iron chlorides (from the liquid that step 4 is obtained) and then pre-concentration are simultaneously based on Fe₂O₃(bloodstone form) extract and Hydrolyze under low temperature, and recovery acid is hydrolyzed from which.Calcining step (step 5), extraction partial exothermic reaction (step 1) and the method The recuperation of heat of other parts is recycled in preconcentrator.

10- can process the solution rich in rare earth element and/or rare metal after bloodstone is removed.As shown in Figure 3, Interior recirculation (after bloodstone is removed) can be completed, the solution rich in rare earth element and/or rare metal can be used for tying The brilliant stage 4.The extraction of rare earth element and/or rare metal can be such as PCT/CA2012/000253 and/or PCT/ Complete described in CA2012000419.The full content of the two documents is incorporated herein by reference in their entirety.

Metal chloride (Me-Cl) such as MgCl of other non-hydrolysables₂Deng then experience following steps：

7- is then at low temperature by the gaseous hydrogen chloride of sprinkling drying and high enrichment in crystallizer by the gaseous state Hydrogen chloride improves the concentration of the solution rich in magnesium chloride and other non-hydrolysable products.This causes MgCl₂Formed with hexahydrate Precipitation, such as after sodium chloride and potassium chloride are removed.

8- magnesium chloride hexahydrates and then calcining are (by rotary kiln, fluid bed etc.), and thus regenerate very high concentration Hydrochloric acid and return it to leach step.

9- other Me-Cl experience standard high temperature hydrolysing steps, can wherein produce mixed oxide (Me-O) and regenerate The hydrochloric acid of azeotropic point (20.2wt%).

NaCl can experience and H₂SO₄Chemical reaction producing Na₂SO₄Azeotrope concentration is equal to or higher than with concentration HCl.Additionally, KCl can experience and H₂SO₄Chemical reaction producing K₂SO₄It is higher than the HCl of azeotrope concentration with concentration.Can be by The charging of sodium chloride and potassium chloride salt aqueous solution as adjusted small-sized chlor-alkali electrolysis pond.In the case of the latter, generate Common alkali (NaOH and KOH) and bleach (NaOCl and KOCl) and HCl.

For example, it is at least concentrated solution of 30wt% that the liquid can be concentrated to iron chloride concentration；Then can be by ferrum chlorine Compound is hydrolyzed at a temperature of about 155 DEG C to about 350 DEG C, while ferric chloride concn is maintained at least level of 65wt%, with The compositionss of the bloodstone comprising liquid and precipitation are generated, and reclaims bloodstone.

For example, it is at least concentrated solution of 30wt% that the liquid can be concentrated to iron chloride concentration；Then can be by ferrum chlorine Compound is hydrolyzed at a temperature of about 155 DEG C to about 350 DEG C, while ferric chloride concn is maintained at least level of 65wt%, with The compositionss of the bloodstone comprising liquid and precipitation are generated, and reclaims bloodstone；And from the liquids recovery rare earth element and/or Rare metal.For example, after the method is further included in recovering rare earth element and/or rare metal, make the liquid anti-with HCl Should be causing MgCl₂Precipitation, and reclaimed.

It will be understood by those skilled in the art, however, that continuation method can process high percentage silicon dioxide (>55%) and The aluminum of impurity and relatively low percentage ratio (for example, as little as about 15%), and remains feasible in economic and technical.Can be right Al₂O₃Obtain gratifying yield (>93-95%), and rare earth element and/or rare metal are obtained and is more than 75%, 85% Or 90% yield.In most of the cases, it is not necessary to heat treatment in advance.Method disclosed by the disclosure can be related to for non- The often extraction of high concentration (strength) and the special technique of acid recovery, thus offer plurality of advantages compared with alkali process.

In step 1, pending material is regardless of whether carrying out that heat treatment is crushed, milling, drying and classification is having There is about 50 μm to about 80 μm of mean diameter.

In step 2, ground material is introduced in reactor, and will experience leaching stages.

The extraction hydrochloric acid for using in step 2 can be from recirculation in step 5,6,8,9,10 and 11 or regeneration (referring to figure 3), its concentration can change from 15wt% to 45wt%.Higher concentration can be come using membrance separation, low temperature and/or high pressure method Obtain.Acidleach is carried can be carried out in pressure and being close at a temperature of its boiling point, thus allow the digestion time of minimum (digestion time) and the extent of reaction (90%-100%) for extending.Extract (step 2) to realize with semi continuous mode, Wherein there is the spent acid of remaining free hydrochloric acid to be replaced by and reacting certain stage or permission acid/mineral ratio reduction The acid of high enrichment, so as to reducing the response time and improving kinetics.For example, kinetic constant k can be：0.5- 0.75g/mole.L.For example, extraction can be continuous extraction.

As noted earlier, alkali metal, ferrum, magnesium, sodium, calcium, potassium, rare earth element and other elements are also by different ranks Section is in chloride form.Silicon dioxide and optional titanium can keep insoluble and will experience (step 3) liquid/solid separation and cleaning Stage.Disclosed method is tended to reclaim chloride in the free hydrochloric acid and solution of the maximum amount of residual to maximize hydrochloric acid The response rate, is classified (rake classifying), belt filter filtration, high pressure, revolving filter centrifugation using such as inclining Deng.Pure SiO₂(extra leaching stages) are cleaned with the nanometer water of purity 99%.The subsequent quilt of not silica containing mother solution Referred to as spent acid (various metal chlorides and water), and enter crystallisation step (step 4).Free HCl and chloride recovery can be with It is at least 99%, 99.5%, 99.9% or 99.99%.

In step 4, then by the spent acid (or lixiviating solution) with a large amount of aluminum chloride with obtain from step 5 or reclaim dry The gaseous hydrogen chloride saturation of dry and high enrichment, or use>The HCl/water solution saturation of 30wt%, this generation aluminum chloride hexahydrate (AlCl₃·6H₂O) precipitate.The precipitate of reservation is then washed and filters or centrifugation, sends into calcination stage (step afterwards Rapid 5).Then remaining spent acid in the 4th step is processed to acid recovery system (step 6 to 8), will wherein obtain pure secondary Product (secondary product).

In steps of 5, aluminum oxide (aluminium dioxide) is directly obtained under hot conditionss.Obtain in gaseous form The hydrogen chloride of high concentration can be supplied to step 4 and 7 for crystallization, wherein which can be processed by hydrophobic membrane.Excessive Hydrogen chloride is absorbed, and as regenerated acid be used for step 2 high enrichment acid, higher than azeotropic point concentration (>20.2%).Example Such as, such concentration can be about 18wt% to about 45wt%, about 25wt% to about 45wt% or 25wt% to 36wt%.Acid also may be used With with gas phase (>30wt%) sour purification is directly re-directed to.

After step 4, various chloride derivatives (mainly ferrum and magnesium and rare earth element and rare metal) are next Experience ferrum extraction step.Such step for example can be carried out by using the technology disclosed in WO2009/153321, its Full content is incorporated herein by.Additionally, bloodstone can add crystal seed for crystal growth.For example, bloodstone draws Crystalline substance can include recirculation seeding.

In step 6, carry out the hydrolysis under low temperature (155-350 DEG C) and generate pure Fe₂O₃(bloodstone) and And regenerated the hydrochloric acid of at least 15% concentration.Method as described in WO2009/153321 process ferrous chloride and iron chloride, its Possible mixture and the solution of free hydrochloric acid, are oxidized to high ferro by series of steps, i.e. preconcentration steps, ferrous chloride The oxidation step of form, and the operating unit for being referred to as hydrolyzer, the wherein concentration of iron chloride is entered finally by hydrolysing step 65wt% is remained, and rich gas vapor of the hydrogen cloride concentration as 15-20.2% is guaranteed to produce concentration, and will experience physics point Pure bloodstone from step.The latent heat of condensation be recovered to pre-concentration and with the excessive heat one from calcination stage (step 5) Rise and be used as to heat input.

Can be partly recycled to from the mother solution (step 6) of hydrolyzer and wherein be observed non-hydrolysable constituent concentration The first step crystallization process of increase.After ferrum is removed, liquid is enriched with other non-hydrolyzable compositions, and mainly includes chlorine Change magnesium or other compositions (various chlorides) and for example still for chloride form rare earth element and rare metal possible Mixture.

The rare earth element and rare metal of chloride form enters hydrolyzer operating unit with percents high enrichment (step 6) (step 10) is extracted from mother solution, wherein various known technologies can be used for extracting this series of single RE-O (dilute Native oxide).Wherein, disclosed method allows, in hydrolyzer, following element is concentrated into high concentration：Scandium (Sc), gallium (Ga), yttrium (Y), dysprosium (Dy), cerium (Ce), praseodymium (Pr), neodymium (Nd), europium (Eu), lanthanum (La), samarium (Sm), gadolinium (Gd), erbium (Er), zirconium And its mixture (Zr).The technology that can be used for Extraction of rare earth element and/or rare metal can be found in the following documents, example Such as, Zhou et al., RARE METALS, Vol.27, No.3,2008, the 223-227 page and US 2004/0042945, which is complete Portion's content is incorporated herein by.It will further be appreciated by those of ordinary skill in the art that can also use to be generally used for extracting from Bayer The various other processes of the rare earth element and/or rare metal of method.For example, various solvent extraction techniques can be used.To certain A little compositions, it is possible to use be related to the technology of octyl phenyl phosphate ester acid (OPAP) and toluene.HCl can be used as remover.This can Effectively to reclaim Ce₂O₃、Sc₂O₃、Er₂O₃Deng.For example, it is possible to the different order for utilizing oxalic acid and metallic iron is used for iron chloride Separate.

The acid pickle rich in increment metal (mainly magnesium) from step 6 and 10 is processed to step 7.The solution is to use From drying and the gaseous hydrogen chloride saturation of high enrichment of step 5, this causes the precipitation of magnesium chloride hexahydrate.For example, Which can be completed with the HCl of the aqueous solution form of more than 30wt%.The precipitate of reservation is supplied to calcination stage step 8, its The pure MgO of middle acquisition (>98wt%), and by the hydrochloric acid of high enrichment (for example, at least 38%) regenerate and be transferred to extraction step Suddenly (step 2).It is using drying gaseous hydrochloric acid from step 8 for step 7 for alternative route.

In step 9, unconverted metal chloride is processed to pyrohydrolysises step (700-900 DEG C), mixed to produce The oxide of conjunction, and can wherein reclaim the hydrochloric acid of 15-20.2wt% concentration.

Another example according to Fig. 3, the method similar to the example shown in Fig. 1, but be able to can include as follows Some variants that face is discussed.

In fact, as shown in figure 3, the method can include returning to knot (after step 6 or only before step 10) The interior recirculation of brilliant step 4.In this case, the mother solution (step 6) from hydrolyzer can be by whole or in part again Step 4 is recycled to, wherein for the non-hydrolysable for including rare earth element and/or rare metal increases into branch's generation concentration.

Such step can be used for the concentration for dramatically increasing rare earth element and/or rare metal, so as to be conducive to them Extraction in step 10.

For step 7, as previously discussed, then pass through at low temperature to spray in crystallizer to dry and high enrichment Gaseous hydrogen chloride and improved the concentration of the solution rich in magnesium chloride and other non-hydrolysable products by the gaseous hydrogen chloride.This can Cause magnesium chloride with hexahydrate form precipitation (for example after sodium chloride and potassium chloride are removed).This can also use aqueous solution shape The HCl of formula is realizing.

As shown in figure 3, extra step 11 can be added.Sodium chloride can be experienced with the chemical reaction of sulphuric acid obtaining sulfur Sour sodium, and regenerate hydrochloric acid of the concentration equal to or higher than azeotropic point concentration.Potassium chloride can be experienced with the chemical reaction of sulphuric acid obtaining Potassium sulfate is obtained, and regenerates hydrochloric acid of the concentration higher than azeotropic point concentration.Sodium chloride and potassium chloride salt aqueous solution can be used as adjusted Small-sized chlor-alkali electrolysis pond charging.In the case of the latter, common alkali (NaOH and KOH) and bleach (NaOCl are produced And KOCl), and other regions (scrubber etc.) of method of disclosure can be used further to a certain extent.

The method that the method for Fig. 8 is also similar to that Fig. 1.Difference between both approaches is step 4 and 5.In fact, In the step of Fig. 8 methods 4 and 5, different metals can be converted to chloride and crystallize (the step of Fig. 8 4), and by calcining And change into oxide (the step of Fig. 8 5).Therefore it will be understood by those skilled in the art that according to the composition of pending material with And the condition of leaching stages, thus different metals can crystallize (the step of Fig. 8 4), and through calcination stage (the step of Fig. 8 5).

It is below non-limiting examples.

Embodiment 1

Aluminium oxide and the preparation of various other products

Used as parent material, clay sample is obtained from the Grande Vall é e regions of Quebec, CAN.

These results represent the meansigma methodss of 80 tests carried out with the sample of each about 900kg.

Just the rough clay of mining state is ground and there is consisting of after classifying：

Al₂O₃：15%-26%；

SiO₂：45%-50%；

Fe₂O₃：8%-10%；

MgO：1%-2%；

Rare earth element and/or rare metal：0.04%-0.07%；

LOI：5%-10%.

Subsequently the material is extracted with the HCl of 18-32wt% at 140-170 DEG C with two benches process.Viscous based on removing Stoichiometric amount required for the acidleach deduction point of soil, using the HCl solution of stoichiometric excess 10-20%.Semicontinuous First leaching stages (step 2) of operation, the hydrochloric acid of clay and a certain ratio of the desired amount of or total amount is contacted 2.5 hours. After removing spent acid, clay is contacted about 1.5 hours at that the same temperature and pressure again with the hydrochloric acid solution of minimum 18wt%.

The typical extraction curve obtained by the single phase extraction of ferrum and aluminum figure 2 illustrates.

Lixiviating solution is filtered, and by solids washed with water, and (the step of referring to Fig. 1 is analyzed with conventional analytical techniques 3).The purity of the silicon dioxide for being obtained is 95.4%, and which does not contain any chloride or HCl.

In another embodiment, by extra leach step, the purity of silicon dioxide is 99.67%.

After extraction and silicon dioxide are removed, the concentration of various metal chlorides is：

AlCl₃：15-20%；

FeCl₂：4-6%；

FeCl₃：0.5-2.0%；

MgCl₂：0.5-2.0%；

REE-Cl：0.1-2%

Free HCl：5-50g/L

Then about the 90% of spent acid gas phase to the about 98% pure hydrochloric acid that dries is crystallized in two stages, and in chlorine Change the ferrum formed in aluminum hexahydrate less than 25ppm.The concentration of the solution (water phase) of HCl be for about 22% to about 32% or 25% to About 32%, make Al₂O₃The response rate be 95.3%.Then crystalline material (the AlCl of hydrate forms that will be reclaimed₃, have 99.8% lowest purity) calcine at 930 DEG C or 1250 DEG C, it is derived from the aluminium oxide of α-form.Allow in 930 DEG C of heating The aluminium oxide of β-form is obtained, and is allowed to obtain α-form in 1250 DEG C of heating.

Another embodiment carries out (decompose at about 350 DEG C and calcine) at low temperature, and the aluminium oxide of alpha form is less than 2%.

To discharge the concentration that the HCl concentration of calcination stage is greater than 30% in gas phase, and crystallize for (recirculation) AlCl₃And MgCl₂.Excessive hydrochloric acid is with needed for leach step and targetedly concentration is absorbed.

Then in view of being extracted as pure bloodstone (Fe₂O₃), iron chloride (ferric form is for about 90-95%) is sent to heat Liquid process.This can be used in the low temperature hydrolysis described by WO2009/153321 and fill from calcining, pyrohydrolysises and leaching stages Divide and reclaim hot technology to complete.

Rare earth element and rare metal are extracted from the mother solution of hydrolyzer, silicon dioxide, aluminum, ferrum, big in hydrolyzer Partial water is removed, and subsequently from hydrolyzer pre-concentration crystallizing.It is apparent that hydrolyzer of the rare earth element in once-through Interior (that is, not concentrating loop) can concentrate average about 4.0 to 10.0 times.Observed in the hydrolyzer (once-through) with Lower enrichment factor：

Ce>6

La>9

Nd>7

Y>9

Remaining magnesium chloride is dried and the hydrochloric acid of high enrichment sprays, and then calcining is MgO, while reclaiming high concentrated acid (such as up to 38.4%).

The pyrohydrolysises of 700-800 DEG C of the mixed oxide comprising other non-hydrolysable components (Me-O) and then experience are anti- Should, and restored acid (15wt%-20.2wt%) delivers to extraction system with variation route.

The gross production rate for being obtained：

Al₂O₃：The response rate of 93.0-95.03%；

Fe₂O₃：The response rate of 92.65-99.5%；

Rare earth element：Minimum 95% response rate (mixture)；

MgO：The response rate of 92.64-98.00%；

The material of discarding：Highest 0-5%；

HCl overall recoverys：Minimum 99.75%；

HCl concentration 15-32% (water) as extraction charging；95% (gas)

Red mud is produced：Nothing.

Embodiment 2

Aluminium oxide and the preparation of various other products

Similar charging (bauxite replacement clay) is processed like that according to embodiment 1, until leaching stages, and show Under conditions of establishing in embodiment 1, which is to be easy to extract.100% extraction ratio is provided to ferrum and aluminum is provided The extraction ratio of 90-95%.The technology is considered as economically viable, and does not produce harmful side product (red mud).Tested Sample there is the Al of variable concentrations₂O₃(up to 51%), Fe₂O₃(up to 27%) and MgO (up to 1.5%).Observe 97.0% gallium extraction ratio.Scandium is extracted as 95%.

Embodiment 3

The enrichment of HCl gases and purification：H₂SO₄Route

H₂SO₄Can be used for carrying out HCl purification.Which can be by using H₂SO₄The dynamic packed column (referring to Fig. 4) of stream adverse current. The HCl of recovery is changed into concentration higher than the HCl of azeotropic point concentration (20.1wt%) and makes the minimum increase of its concentration by this permission About 60% to about 70%.

Water is by H₂SO₄Absorb, and subsequently apply H₂SO₄Regeneration, wherein makes H₂SO₄Return to about 95% to about 98wt% dense Degree.It is recycled back in the release water (water release) of this stage not sulfur-bearing, and for crystallizing dissolving etc..Post is filled out Filling thing can include polypropylene or PTT (PTT).

Burning capacity can be carried out together with heating by the exhaust gases air and oxygen concentration.Oxygen concentration：+ 2% represents flame temperature Degree increased 400 DEG C of highest.

Embodiment 4

The enrichment of HCl gases and purification：Calcium chloride is to calcium chloride hexahydrate (absorption/desorption process)

As shown in figure 5, CaCl₂Can be used for drying HCl.In fact, CaCl₂Can be used for what absorption included in HCl Water.In this case, CaCl₂It is converted to the form (CaCl of its hexachloride₂·H₂O), and a saturation system most Egress changes regeneration mode into, the hot-air for wherein reclaiming from the calcining waste gas of aluminium oxide and magnesium oxide spray roasting be introduced into Regeneration fixed bed.Or, other absorbent such as LiCl can be used to replace CaCl₂.Such ion/crossover process can be with Referring to Fig. 4, and circulation reversion can be made to switch to another post from a post.

It will be appreciated by those skilled in the art that the process described in embodiment 3 and 4 can be come in a variety of ways Use.For example, the various methods that these methods can be proposed with the disclosure are combined.For example, such purification technique can with Fig. 1, 3rd, 6 to 8, the method integration shown in 10A, 10B, 11A and 11B.For example, these technology can be used in selected from step 5,6,8,9,10 Downstream (referring to Fig. 1 and 3) with 11 at least one step.Which may be also used in the downstream of step 4 and/or step 7.Which may be used also To be used in the downstream (referring to Fig. 6) of at least one step selected from step 104 to step 111.

Embodiment 5

Aluminium oxide and the preparation of various other products

The embodiment is carried out by using the method shown in Fig. 6 and Fig. 7.It should be noted that the side shown in Fig. 6 and Fig. 7 Method difference is only that Fig. 7 illustrates other stage, i.e. stage 112 and 113.

Prepared by raw material

Raw material, such as clay, are with secondary breaker process in clay Preparation equipment 101.In vertical roll grinder (example Such as Fuller-Loesche LM30.41) in dry-basis dry grinded and be classified.Clay prepares 101 includes three rollers Grinding machine；Two capacity with about 160-180tph run, and one standby.If desired, raw material can be reduced to 85% raw material It is less than 63 μm.Material through processing is then stored in homogenizing silo, is supplied to sour extraction equipment 102 afterwards.Table 1 below is shown The result gone out obtained in the stage 101.If Ore includes element fluorine, then can apply spy before carrying out for 102 stages Different process.In presence of hydrochloric acid, fluorine can produce Fluohydric acid..This sour corrosion is extremely strong, and damages health.Therefore, soak Before carrying 102, optional process fluorine can be completed and separate 112.Stage 112 can be included in during pre- extraction is processed with acid treatment come From the material through processing in stage 101, so as to remove Fluohydric acid..Therefore, according to the composition of raw material, fluorine separation phase can be carried out 112 (or pre- leaching stages 112).

Table 1

Acidleach is carried

Then, in 80m³Acidleach is semi-continuously carried out in glass lined reaction vessel carries 102.Semi-continuous mode is included in the reaction phase Interior use high concentration regenerated acid substitutes 1/3 acid that reacted, and which greatly improves kinetics.Reactor arrangement includes example Such as a series of three reactors.Other embodiments are had been carried out, under 1atm, wherein carries out the first extraction, Ran Houyong HCl/water solution or gaseous state HCl carry out second and the 3rd semicontinuous or continuous extraction.

Under high temperature and high pressure (about 160 DEG C to about 195 DEG C and pressure about 5barg to about 8barg) it is fixed extraction Period.Response time be target response degree (for Al₂O₃For 98%), extraction pattern, acid concentration (acid strength) with And the function of the temperature/pressure for applying.

The spent acid of 102 recovery and then filtration 103 from unreacted silicon dioxide and Titanium Dioxide are carried from acidleach, and is led to Automatic pressure filter washing is crossed, wherein all free HCl and chloride are all recovered.This permission such as maximum is for about 30ppm's SiO₂Enter waste liquid.Then ≈ 96%+SiO are produced₂The cleaning silicon oxide of concentration.Various selections are likely in this. For example, 96% silicon dioxide finally can be neutralized by alkaline bath, cleaning and then briquetting before storing.According to another In one embodiment, by increasing another leach step, being subsequently to ensure that removal TiO₂Solid isolation steps carry out purification two Silicon oxide (stage 113 in referring to Fig. 7).Under this special case, high-purity silicon dioxide 99.5%+ is produced.In the stage In 113, titanium and silicon can be separated each other in every way.For example, the solid for obtaining from the stage 103 can be in MgCl₂Presence Under less than extracting at a temperature of 90 DEG C or 80 DEG C and under low acid concentration.For example, acid concentration can be less than 25% or 20%. The acid can be HCl or H₂SO₄.In this case, after titanium is maintained at this extraction be solvable, and titanium still be solid Form.Thus these solids obtained after stage 113 and liquid separate to provide final TiO₂And SiO₂.Water input and two Silicon oxide cleaning stream is 1:Ratio (the 150t/h SiO of 1 (silicon dioxide/water)₂/150t/h H₂O), but including during described Closed-loop path in washing water circulation and for finally cleaning silicon dioxide and for reclaim leaching stages generate institute There is the process water of the limited quantity of chloride and free HCl.The result obtained during stage 102 is shown in table 2 below.

Table 2

AlCl₃·6H₂O is crystallized

There is the spent acid of the chlorination aluminium content of about 20% to about 30% and then process in crystallization stage 104.Dry and high Degree concentration HCl (>90wt%) it is sprayed in two benches crystallization reactor with gas phase, the knot of this permission aluminum chloride hexahydrate Brilliant.

Acid is for about 600m by the flow velocity of these reactors³/ h to about 675m³/ h, during the highly exothermic reaction, reaction Device is maintained at about 50 DEG C to about 60 DEG C.Heat is reclaimed, and is exchanged to 107 part of sour purification of equipment, the heat so as to ensure appropriate is passed Lead and minimize the heat loss of equipment.Relative to other compositions, with the increase of HCl concentration of dissociating in crystallization reactor, chlorination Aluminum dissolubility reduces rapidly.For precipitation/crystallization, AlCl₃Concentration be for about 30%.

Therefore, the HCl concentration in crystallization process is for about 30wt% to about 32wt%.

Hydrothermal solution acid-recovery plant 105 is then passed to from the aqueous solution of crystallization stage 104, and in calciner 106 The crystal is processed by decomposition/calcination stage.

One-step crystallization stage or multiple steps of crystallization stage can be completed.For example, it is possible to carry out the two-step crystallization stage.

The result obtained during the stage 104 is illustrated in table 3 below A and 3B.

Table 3A

Table 3B

Calcining and hydrothermal solution acid recovery

Calcining 106 is included using the two benches recirculating fluidized bed (CFB) with pre-heating system.Pre-heating system can include etc. Gas ions torch is processed with heating steam.Which processes the crystal of decomposition/calcination stage.Grasp at a temperature of about 350 DEG C Most of hydrochloric acid is discharged in the first stage of work, and second stage is calcined.Acid from two stages (is returned from the process 68%) about the 66% of the acid of receipts to about and then being recovered and deliver to acidleach and carry 102 or to sour purification 107.In about 930 DEG C of temperature In the second reactor of lower operation, acid is reclaimed by condensing in two posts and absorbing, and main use is carried from acidleach The washings in portion 102.Latent heat from the part is reclaimed simultaneously with substantial amounts of water, be which has limited water and is input into only.

In iron oxides production and 105 system of acid recovery, it is pre- which includes making the aqueous solution from crystallization 104 to experience first Enriching stage, is subsequently processed in hydrolysis reactor.Herein, produce during bloodstone is K cryogenic treatment (about 165 DEG C).Follow again Then loop back path is taken from hydrolyzer and is recycled to preconcentrator, makes the concentration of REE, Mg, K and other elements.The recirculation Loop allows rare earth element chloride and/or the concentration of rare metal chloride and various metal chlorides to increase, and at certain These products and bloodstone coprecipitation need not be made in degree.

According to acid balance in a device, restored acid was transmitted directly to for 102 or 107 stages.Table 4 was illustrated in the stage 105 In the result that obtains.

Table 4

Table 5 shows the result obtained in the stage 106.

Table 5

Rare earth element and rare metal are extracted

Then, in order to rare earth element and rare metal extract 108, the steam obtained from 105 recirculatioies is processed, wherein will Remaining ferrum is reduced to ferrous irons (Fe²⁺), then carry out a series of solvent extraction stage.Reactant is oxalic acid, NaOH, DEHPA (two-(2- ethylhexyls) phosphoric acid) and TBP (three-normal-butyl phosphate ester), organic solution, kerosene and HCl are used for rare earth unit Plain chloride and rare metal chloride are converted into hydroxide.The solution that adverse current organic solvent is peeled off using HCl, subsequently into The specific sintering of the rare earth element and rare metal of hydroxide form, and change into highly purified respective oxide.Ion Switching technology can also realize the identical result with PTT (PET) film.

The use speed of the iron powder or old metal from 105 such as FeO can depend on the Fe in mother solution³⁺Concentration.Molten in REE Agent is extracted (SX) and separates and extract the HCl that may need 1tph speed in rare earth element and/or rare metal oxalates again (100wt%) as stripping solution.

Larger numbers of water (softened water or nanometer water) is added the stripping solution with the speed of 100tph and washs precipitation Thing.

The oxalic acid of two-hydrate forms is added with the speed of 0.2tph and contributes to rare earth element and rare metal oxalates Precipitation.NaOH or MgOH can be used as nertralizer with the speed of 0.5tph.

DEHPA SX organic solutions are used as the active agent in rare earths separation with the speed of 500g/h, and by TBP SX organic solutions are used as gallium with the speed of 5kg/h and reclaim the active agent in separating with yttrium.Finally, by kerosene diluent with about The speed of 2kg/h is used for all SX parts.It is calcined through indirectly heat and occurs, in electronic rotation stove, inclusions to be converted For REE₂O₃(oxide form), and keep product purity.

The result of the various tests that is done with regard to the stage 108 is shown in Table 6.

A circuit is separated in branch (5) with the following element of solvent extraction and separation：

·Ga₂O₃

·Y₂O₃

·Sc₂O₃

·Eu₂O₃+Er₂O₃+Dy₂O₃

·Ce₂O₃+Nd₂O₃+Pr₂O₃

Total recovery：84.53%

Or, can carry out the stage as described in PCT/CA2012/000253 and/or PCT/CA2012000419 108.

Solution after stage 108 and 109 mainly includes MgCl₂、NaCl、KCl、CaCl₂、FeCl₂/FeCl₃And AlCl₃ (trace), then experiences the stage 111.As Na, K, Ca of MgO can be carried by being crystallized with particular order in the stage 110 Take；It is Na first, next to that K, followed by Ca.This technology can be used for such as Israel's dead sea salts processing plant to produce MgO simultaneously removes alkali from raw material.

Observe that the recirculation circuit of Fig. 7 allows GaCl₂And ScCl₂Concentration and not with bloodstone coprecipitation.This steam is right By REE/RM extractions are gone through, it is followed by a series of solvent extraction stages and is converted into highly purified each autoxidisable substance.REE elements Overall recovery reach：For Ga is 84%, for Sc is 95% and for remaining REE element that low amounts is present is 68%.

HCl regenerates

Alkali (Na, K), once crystallization, then be sent to for reclaiming the alkali salt acid regeneration equipment of the hydrochloric acid (HCl) of high enrichment 110 and processed wherein.Select to produce value added product for the method for converting.

Various selections can be used to convert NaCl and KCl, and be intended to reclaim hydrochloric acid.One embodiment can by its with highly dense Sulphuric acid (the H of contracting₂SO₄) contact, this produces sodium sulfate (Na respectively₂SO₄) and potassium sulfate (K₂SO₄), and regenerate concentration and be higher than The HCl of 90wt%.Another embodiment is to use sodium chloride and potassium chloride salt aqueous solution as adjusted small-sized chlor-alkali electrolysis The charging in pond.In the case of the latter, common alkali (NaOH and KOH) and bleach (NaOCl and KOCl) are produced.In different electricity The electrolysis of NaCl and KCl saline is completed in pond, and wherein electric current is adjusted to the chemical reaction needed for meeting.In both of these case Under, which is two step process, wherein saline experience high current.And alkali (NaOH or KOH) and chlorine (Cl₂) and hydrogen (H2) produce together Raw.H₂And Cl₂Then conventional flame is experienced, the acid gas (100wt%) of high enrichment is wherein produced and is used directly for tying The brilliant stage 104, or for needing the crystallization stage of the acid of dry high enrichment.

Magnesium oxide

Then, most of composition (such as AlCl is substantially free of₃、FeCl₃, REE-Cl, NaCl, KCl) but be rich in MgCl₂'s Stream through reducing is sent to oxidation magnesium apparatus 111.In MgO, MgCl₂Pyrohydrolysises and any other remaining impurity turned Chemical conversion oxide, while regenerated acid.The first step is preevaporator/crystallizer stage, wherein calcium be removed and by with sulphuric acid Simple chemical reaction and change into Gypsum Fibrosum (CaSO₄·2H₂O), which needs to separate MgO.Which increase the capacity of MgO roastings simultaneously Also somewhat increase energy resource consumption, while reclaiming substantially HCl.Following step is come specific pyrohydrolysises by spray roasting MgO concentrated solutions.Generate two (2) primary products；The MgO being further processed, and HCl (about 18wt%), which is recycled Return upstream leaching stages 102 or hydrochloric acid to cleanse equipment (107).The MgO products for deriving from spray roasting stove may be needed into one Step washing, purification and final calcining, depending on target quality.Purification and calcining can include washing-hydration step and mark Quasi- calcining step.

It is elevated chemical activity from the MgO of spray roasting stove, and is directly loadable into water tank, which is reacted with water To be formed in the magnesium hydroxide of dissolubility difference in water.The trace chloride of residual, such as MgCl₂, NaCl, be dissolved in water.Mg(OH)₂Outstanding After supernatant liquid is precipitated in concentrator, the vacuum drum filter for removing residual water is marched to forward.The Mg (OH) of cleaning₂Then Calcination reactor is marched to forward, wherein makes which high temperature is exposed in vertical multistage stove.Water is discharged from hydrate, and allow Mg(OH)₂It is changed into MgO and water.In this regard, magnesium oxide have high-purity (>99%).

HCl purification

The HCl that 107 effective purification of hydrochloric acid purification phase is regenerated from different piece (such as 105,106,111), and increase Its purity for crystallization, and dry high enrichment acid (>90wt%) can serve as spraying reagent.Stage 107 also allows Control returns to the concentration (about 22wt% to about 32wt%) of the acid in stage 102 and allows the balance of total acid and water.Complete total Equipment level weighing apparatus is mainly by being further used as absorbing medium by washings, the dissolving as quencher or as crystallization stage is situated between Matter.For example, the stage 107 can be implemented by using the process shown in Fig. 4 or Fig. 5.

For example, purification can be carried out by Membrane Materials process.The Membrane Materials process for adopting herein is when with different temperatures Two kinds of waterborne liquids by hydrophobic film separate when occur.The driving force of the process is by the temperature between these solution Vapor partial pressure difference that gradient is caused is providing.Steam enters cold side from warm skidding.It is not intended to be constrained by the principle, separation mechanism It is the vapour/liquid balance of the liquid mixture based on HCl/ water.The practical application of such technology has been used to HCl/ water, H₂SO₄/ water System, and also be the sodium-chloride water solution for obtaining drinking water from sea water for purpose with big commercial scale, and nanometer is aquatic Produce.Therefore, Membrane Materials are based upon the separation process of the evaporation of porous hydrophobic membrane.The process is carried out at about 60 DEG C, and is led to Internal water circulation loop is crossed from 104 and 102 stage efficient recovery heats, so as to the film is kept constant entrance temperature.For example, may be used To use 300,000m²8 films of equivalency tables area/film, are substantially higher than ≈ 750m to obtain³The azeotropic point of/h is (i.e.>36%) HCl concentration, then obtains last 90% concentration by pressure distillation (rectifying column).

Thus regenerated acid is processed by hydrophobic membrane and water is separated with HCl, so as to purification HCl；Therefore, HCl concentration is increased Add to and be up to about 36% (more than azeotropic point), therefore allow to obtain in gas phase by the single phase rectification of pressure stripper> 90%, (spray) for crystallized region；Therefore the acid concentration for entering crystallization stage is controlled to up to 30-35% (aqueous solution).

As noted, the stage 107 is operated at about 60 DEG C, and is carried by the heat reclaimed from the stage 102 to 110 Heating load is input into.Rectifying column is operated in about 140 DEG C in reboiler section.Net energy demand be zero (its actually negative value ,- 3.5Gj/t Al₂O₃), because the two systems are all in balance (equilibrium) and balanced (balance).

For example, sour purification can be by being carried out using adsorption technology on activated alumina bed.In continuous mode, need Want at least two adsorption towers to realize absorption and regenerating in another wherein in one wherein.Regeneration can pass through with adverse current Mode supplies hot gas or depressed gas to carry out.The technology will obtain the purified gases of 100wt%.

For example, sour purification can by using calcium chloride as water entrainer carrying out.Dilute hydrochloric acid solution by post with Dense calcium chloride solution contact.Then water is removed from hydrochloric acid solution, and 99.9% gaseous state HCl is escaped from the process.Will be cold But water and cryogenic coolant are used for the trace water being condensate in HCl.Dilute CaCl₂Solution is by assuring that the vaporizer of calcium chloride recovery And concentrate.According to the impurity in the HCl solution charging entered in tower, some metals may pollute calcium chloride concentrate solution.With Ca (OH)₂Coprecipitation and filtration allow to remove these impurity.The post can be operated for example under 0.5barg.The technology can permit 98% HCl is reclaimed perhaps.

Table 7 illustrates the result that the method shown in Fig. 6 is obtained.

Table 8 to 26 illustrated compared with industrial standard, the result obtained by product prepared by the method according to Fig. 6.

Table 8

P₂O₅Removal technology can include precipitating phosphorus with Disulfatozirconic acid. for example after extraction.Which is may be prescribed as example in vacuum Under in 80 DEG C to about 90 DEG C or about 85 DEG C to about 95 DEG C heating solution in.

Table 9

Table 10

Table 11

* material can be fabricated to brick

Table 12

Note：Product can have unbleached cellulose fiber filter aid.Cellulose wood powder.

Table 13

Table 14

Table 15

Table 16

Table 17

Table 18

Table 19

Table 20

Table 21

Table 22

Table 23

Table 24

Table 25

Table 26

In order to demonstrate the versatility of disclosed method, some other tests are made, so as to prove that these methods can It is applied to various raw material sources.

Embodiment 6

Another parent material has been used for preparing the acidic composition comprising various components.In fact, for rare earth element and The material of rare metal (being especially enriched in zirconium) concentrate has been tested by.Table 27 be shown with Fig. 1,3,6 and 7 Suo Shi and real The result extracted by the similar approach described in detail by example 1,2 and 5 is applied to such parent material.Therefore, it can from shown in table 27 As a result infer, present in extraction, various component (various metals such as aluminum, ferrum, magnesium and rare earth element and rare earth metals) can To be extracted from the extraction compositionss for being obtained, and they may finally pass through disclosed method, such as embodiment 1,2 With 5 in the method that presents separating.

Embodiment 7

To carry out other tests with the similar fashion described in embodiment 6.In the present embodiment, carbonate has been used as initial material Material.(referring to table 28 below).

The test done by 27. pairs of materials rich in zirconium of table

The test done to carbonate rock by table 28.

Therefore, it can infer that extracted present in the extraction compositionss for being obtained is each from the result shown in table 28 Planting metal, rare earth element and rare metal can be eventually through the side presented in disclosed method, such as embodiment 1,2 and 5 Method is separating.In this case, the parent material be used for Fig. 1,3,6,7,8, the process of 10A, 10B, 11A or 11B.

Embodiment 8

Red mud is tested as parent material.The HCl of 6M concentration is used for extracting red mud (RM) sample.As a result show In table 29 below to 35.

29. red mud extracting condition of table

30. red mud leaching results of table

The composition of table 31.RM A

	Al	Si	Fe	Ca	K	Mg	Na	Ti
									%	10.2	4.59	16.4	2.71	0.01	0.02	3.07	2.6
Kg	80.9166	36.41247	130.1012	21.49843	0.07933	0.15866	24.35431	20.6258

The composition of table 32.RM B

	Al	Si	Fe	Ca	K	Mg	Na	Ti
									%	10.9	5.66	17.2	1.72	0.01	0.03	5.05	2.62
Kg	86.4697	44.90078	136.4476	13.64476	0.07933	0.23799	40.06165	20.78446
									%	0.69	19.8	1.37	0.06	0.01	0.01	0.01	11.2

The composition of table 33RM1

	Al	Si	Fe	Ca	K	Mg	Na	Ti
									%	8.85	4.76	18.5	4.04	0.05	0.03	2.82	2.36
Kg	213.108	114.6208	445.48	97.2832	1.204	0.7224	67.9056	56.8288

The composition of table 34.RM1 (2), RM1 (3), RM1 (4), RM1 (5) and RM1 (6)

	Al	Si	Fe	Ca	K	Mg	Na	Ti
									%	8.85	4.76	18.5	4.04	0.05	0.03	2.82	2.6
Kg	213.108	114.6208	445.48	97.2832	1.204	0.7224	67.9056	62.608

Table 35.RM2, RM2 (2), RM2 (3), RM2 (4), RM2 (5), the composition of RM2 (6) and RM2 (7)

	Al	Si	Fe	Ca	K	Mg	Na	Ti
									%	10.9	5.66	17.2	1.72	0.01	0.03	5.05	2.62
Kg	230.971	119.9354	364.468	36.4468	0.2119	0.6357	107.0095	55.5178

Embodiment 9

Table 36 and 37 summarizes the chemical total size of the residue (from the red mud of country variant) through processing.These analyses It is by independence and the laboratory of certification is carried out.

Table 36

Table 37

It can thus be seen that red mud is successfully extracted with HCl, therefore for the recovery of various components present in red mud Allow good yield.Present in the lixiviating solution for being obtained, these various products or component therefore can be by the disclosure The previous indication of method as carry out separating and final change.The lixiviating solution of acquisition can be as described by disclosed method Processed like that.The leaching stages of embodiment 8 can be considered as the leaching stages 2 of such as Fig. 1 or Fig. 3；Leaching in Fig. 6 or Fig. 7 Carry the stage 102；The leaching stages 2 of Fig. 8, the extraction 202 of Figure 10 A, extraction 302 of Figure 11 A etc..For example, obtain in embodiment 8 Lixiviating solution can be processed as shown in Fig. 1,3,6 to 8,10A, 10B, 11A and 11B.For example, the lixiviating solution can be with Processed as described in embodiment 1,2 and 5.

Fig. 9 illustrates the method for separating Si and Ti.For example, when Ore is used as parent material, extraction can be in chlorine Carry out in the presence of gas, so as to keep Ti to be in TiCl₄Form, because which keeps in the solution, and Si keeps solid (SiO₂).So Afterwards, Ti can be injected into plasma torch for purification.

Whenever necessary, the institute of the disclosure can be used for separately the two objects for such method of purification Si and Ti There is method.Stage 113 for example, referring to Fig. 7.

Method shown in Figure 10 A/10B and 11A/11B is its that can be used to processing comprising such as Mg and such as Ni and/or Co The method of the various materials of its metal.These materials can also include other metals, aluminum, ferrum etc..Therefore these methods may be used With effective for processing red mud.Figure 10 A/10B are similar with the method for Figure 11 A/11B, and institute's difference is in Figure 10 A/ After the step of 10B 204, magnesium retains in the solution (referring to step 211), and 304 the step of Figure 11 A/11B after magnesium sunk Form sediment (referring to step 311).

The step of other methods that some steps carried out in the method for Figure 10 A/10B and 11A/11B are described with the disclosure Similar.

For example, step 201 is similar with the step of Fig. 6 and 7 101 with 301.Additionally, the step of Figure 10 A/10B and 11A/10B 202 is similar with the step of Fig. 6 and 7 102 with 302.

Figure 10 A/B are similar with the step of Fig. 6 and 7 103 with 303 with the step of 11A/B 203.

The step of Figure 11 and 12 213, is similar with the step of Fig. 7 113 with 313.For step 214 and 314, TiO₂Can be most The whole purification by plasma torch.

Finally, CaSO₄·2H₂O (Gypsum Fibrosum) can as step 223 and 323 describe in detail as produce.Finally, according to step 224th, 324,225 and 325, Na can be produced₂SO₄And K₂SO₄.

For step 213 and 313, TiO₂Titanium chloride can be converted into, so as to dissolve in the liquid phase titanium.For example, this can With by making TiO₂With Cl₂Complete with carbon (C) reaction.Therefore, SiO₂Can be with separated from one another, because SiO with titanium₂Keep solid, And titanium chloride is dissolved.For example, it is possible to carry out step 213,313,214 and 314 as Fig. 9 is described in detail.

Such method also effectively realizes the full recovery of HCl.

According to Ni and/or Co precipitations (step 212), LiOH can be precipitated and final washing in a step 208, and Ni and Co is right The purification by solvent extraction 207 afterwards.Those skilled in the art are thus, it is possible to select the felicity condition for both metals of separation. The example of such different modes of Ni and Co is separated disclosed in US2011/0283838, entire contents are incorporated by reference into Herein.Then, further extraction can be carried out in step 209, so as to further extract metal.

After 304 the step of being related to MgO and separating, LiCl can be crystallized and be washed (stage 308).After step 305, Obtain bloodstone and precipitate Ni and Co (stage 312).Ni and Co are may then pass through using mentioned upper during the description stage 207 State technology (solvent extraction) and separated from one another.

For example, if the parent material for being ready to use in the method for Figure 10 A, 10B, 11A and 11B includes aluminum, then can carry out Step 210 and 310 is with precipitate A lCl₃.Such step (210 or 310) is similar with the step of carrying out in Fig. 6 and 7 104.With class As mode, Figure 10 A, 10B, 11A are similar with the step of Fig. 6 and 7 105 with 305 with the step of 11B 205.Figure 10 A, 10B, 11A Similar with the step of Fig. 6 and 7 106 with 306 with the step of 11B 206.The HCl purification that carries out in step 215 and 315 and Fig. 6 and The step of carrying out in 7 107 is similar to.Such as Figure 10 A, 10B, 11A and 11B 216 and 316 are visible, thus regenerate HCl.

Alternatively, the group of foundation step 209 and the parent material according to the method for Figure 10 A, 10B, 11A and 11B Into step 210 and 310 can be omitted or bypass.Therefore, if parent material is substantially free of aluminum, or if step 209 it The content of aluminum is at a fairly low afterwards, then can carry out step 249.Then, according to the step of Figure 10 A, 10B, 11A and 11B 249 With 349 (wherein obtaining the mixture of various metal chlorides), can be calcined in step 217 and 317, so as to finally obtain Obtain the mixture of various metal-oxides.

The impurity obtained in step 210 and 310 can be crystallized in step 218 and 318.By doing so it is possible, can tie Brilliant NaCl (step 219 and 319) and KCl (step 221 and 321).Electrolysis NaCl (step 220 and 320) and KCl (step 222 and 322) can carry out as pointed by the disclosure is previous.

Disclosed method provides multiple advantages and difference relative to known method.

Disclosed method provides totally continuous economic solution, and which can successfully from polytype material Middle extraction aluminium oxide, while the ultrapure secondary species of high value-added is provided, including the rare earth element and rare earth metal of high enrichment.? Technology described in the disclosure allows total acid recovery of innovation amount, also makes restored acid have ultrahigh concentration.When by its with semicontinuous When leach extraction method is combined, be conducive to very high extraction ratio and allow crystal aluminum chloride and concentrate the specific of other increment compositions Method.These methods also allow to prepare aluminum using produced aluminium oxide.

Another advantage of disclosed method is high temperature and the high combination for entering concentration of hydrochloric acid.With wherein systematically using trip From HCl driving forces semicontinuous operation combine, less than basic batch processes reference time about 40% time in, ferrum and The extraction ratio of aluminum respectively reaches 100% and 98%.The higher another advantage of HCl concentration ratio azeotropic point concentration is that capacity increases Potentiality.Additionally, HCl concentration ratios HCl azeotropic point concentration is higher and semicontinuous method represents the important advance of this area.

It is belt mistake for the another advantage in leaching stages countercurrent washing Mother liquor technology detached with silicon dioxide Filter provides purity expection ultra-pure silicon dioxide of the purity more than 96%.

Using drying, cleaning and high enrichment gaseous state HCl as sprinkling reagent come by AlCl₃Crystallize into AlCl₃· 6H₂O, it is allowed to only include the pure aluminum chloride hexahydrate of the ferrum and other impurity of a few millionths.Can need minimal number of Stage is allowing appropriate crystal growth.

With by AlCl₃·6H₂O is sintered into Al₂O₃The direct interconnection of (this generates the gas of very high concentration) is allowed in knot Accurate continuous adjustment hydrochloric acid concentration in brilliant device, and thus suitable control crystal growth and crystallization process.

Thus applicant also proves their method effectively separating red mud (or selected pending material) successively Each valuable and vendible component and reclaim used acid.Therefore these methods allow to reclaim in Bayer process generally The most aluminium oxide for wasting.

Thus disclosed method provides the solution of uniqueness for these large-scale red mud ponds, remedies and simultaneously because reclaims The simultaneously aluminium oxide and other value added products of purification are separated via the acid regeneration stage and allows rapid investment to return.These results show Disclosed method represent innovation and economy technology, its be not only will not produce red mud by multiple aluminum ores produce aluminium oxide Viable option, but also be to remedy existing red mud toxic residua (to which represent the environmental protection of aluminium oxide and aluminum i ndustry Responsibility) means.

Although the initial composition of red mud can change according to bauxite source, operating condition etc.；But disclosed method can So that the feedstock of various compositions is setup flexibly.This can process the red mud from any alumina producer.Successfully test Different red mud sources from different parts of the world.

Applicant has now been found that fully-integrated and continuous method, and substantially all reclaims for from each comprising aluminum Plant alumina-bearing material (clay, bauxite, alumino-silicate materials, slag, red mud, flying dust etc.) and extract aluminium oxide and other value added products Hydrochloric acid.In fact, the method allows to produce substantially pure aluminium oxide and such as purification silicon dioxide, pure bloodstone, titanyl Compound, other pure mineral are (for example：Magnesium oxide), other value added products of rare earth element and rare metal product.Additionally, the party Method does not require the Grape berry before sour leaching step.Acidleach is carried using with high pressure and temperature conditionss and very high regeneration The semicontinuous technology of concentration of hydrochloric acid is carrying out.Additionally, the method does not produce not salable any residue, it is thus eliminated that Such as in the case of alkali process environmentally harmful residue.

The advantage in high-temperature calcination stage, in addition to allowing the α-type aluminium oxide needed for control, also effectively provides than altogether The higher aqueous solution form hydrochloric acid of boiling point HCl concentration concentration (>38%), the higher entrance of leaching stages is thus provided that HCl concentration.The hydrochloric acid network of calcination stage with two (2) crystal system interconnections, and can be adjusted by pressure, excessive HCl Can be absorbed with concentration of aqueous solution as high as possible.Have six chloride monohydrates and low moisture content (<2%) raw material is entered The advantage of (incoming feed) is to allow the continuous acid for reclaiming the concentration higher than azeotropic point concentration.Three of methods described (3) this HCl balances and double duty in regular section and more than the azeotropic point is an impressive progress of this area.

Another advantage is will to enter chemicals (iron chloride) to be used for iron oxides and HCl recovery unit, wherein from any The all excessive heat that calcining part, pyrohydrolysises and extraction part are loaded into is recovered and includes metal chloride with pre-concentration Mother solution, so that hydrolyze the iron chloride of very pure bloodstone form in very low temperatures and with dense with azeotropic point identical Degree regenerated acid.

The another major advantage of the current method of iron chloride hydrolysing step be in the hydrolyzer reactor by hydrolyzer and Home loop between crystallization, with the probability of the rare earth element of very high concentration concentration chloride form.The advantage is Disclosed method is benefited from each step of application gradual change cocnentration factor.Therefore, in this stage, except internal concentration loop Outside, with silicon dioxide, aluminum, ferrum and have be close to saturation (substantial amounts of water evaporation does not have free hydrochloric acid) balance molten Liquid also allows for bringing rare earth element and non-hydrolyzable element into entrance raw material with a few millionths, and after iron chloride is removed Which is directly concentrated with high percentage in hydrolyzer.Then, when in percentage of water at ordinary times, particular oxides (RE-O) pure Changing can be carried out using various technology.Advantage is doubled herein：Using integrated processing stage concentration very high-caliber rare earth unit Element, and above all the method prevents from making that the spent acid main flow after leach step is (very dilute) that there is pollution aluminum chloride master Therefore stream simultaneously affect Al₂O₃The risk of yield.Another improvement of this area is the selective removal in addition to being fully integrated Component allows for rare earth element to be condensed into relatively high concentration (percentage ratio).

Another advantage of the method is to take the salt of self-alumina calcining step or magnesium oxide dinectly bruning again by sprinkling Acid carrys out selective crystallization MgCl₂, wherein produce the acid of the high enrichment of gas phase or aqueous solution form in both cases.According to chlorine Change the specific crystallization of aluminum, (about 85wt% to about 95wt%, about 90wt% is extremely for the direct interconnection with calcination reactor, very high concentration 95wt% or about 90wt%) HCl gases allow based on desirable oxidation magnesium quality continuously accurately adjusting crystallizer.The method The step of (MgO production or other increment metal-oxides) need based on enter process raw material chemical property, then at this After individual extra step, complete rare earth element and rare metal extracts point；Its advantage is the extra concentration effect of application.

Pyrohydrolysises allow any residue muriatic final convert and produce can serve as fertilizer refine oxide ( In the case of clay is as parent material), and allow to process a large amount of washings from procedure below, the process has to be used for soaking Recovery hydrochloric acid in the closed-loop path of the azeotropic point for putting forward step.The advantage of this final step is related to following facts, i.e. which is complete The treatment loop of closure acid recovery simultaneously guarantees not producing environmentally harmful residue when any kind of raw material is processed, such as Front described.

It is that fully-integrated method proposed by the disclosure is actual to the main contributions of this area to allow at economized form Reason bauxite, while do not produce red mud or the Harmful Residue.(any suitable containing aluminum except can be used for other natural raw materials Material or aluminum ore) the fact outside, using reclaim completely and total concentration (for example, about 21% to about higher than azeotropic point concentration 38%) the value-added secondary species of hydrochloric acid, selective extraction and to the adaptation of environmental requirement (while protecting in terms of improvement cost Hold great competitiveness), represent the major advantage of this area.

Therefore, this is shown present disclose provides preparing pure alumina with HCl treatment and while producing high-purity and Gao Pin The product (mineral) of matter the fully-integrated method of Extraction of rare earth element and rare metal.

Although description is made with reference to specific embodiment, but it is to be understood that changing in a large number to those skilled in the art is Obviously.Therefore, foregoing description and accompanying drawing should be considered specific example, and and unrestricted.

Claims

1. the method for being used for processing red mud, methods described include：

With HCl extraction red muds to obtain comprising aluminum ions lixiviating solution and solid at a temperature of 125 DEG C to 225 DEG C, and The solid is separated with the lixiviating solution；

Make the lixiviating solution react with HCl to obtain the liquid comprising iron ion and include AlCl₃The described aluminum ions of form is sunk Starch, and the precipitate is separated with the liquid；And

Effectively by AlCl₃Change into Al₂O₃Under conditions of heat the precipitate, and the gaseous state produced by optionally reclaiming HCl.

2. the method for claim 1, wherein concentration extract the red mud for the HCl of 25wt% to 45wt%.

3. the method for claim 1, wherein under the pressure of 50psig to 150psig concentration be 25wt% extremely The HCl of 45wt% extracts the red mud.

4. the method for claim 1, wherein at a temperature of 160 DEG C to 190 DEG C concentration be 25wt% extremely The HCl of 45wt% extracts the red mud.

5. the method for claim 1, wherein at a temperature of 160 DEG C to 175 DEG C concentration be 25wt% extremely The HCl extraction red muds of 45wt%.

6. the method for claim 1, wherein at a temperature of 185 DEG C to 190 DEG C concentration be 25wt% extremely The HCl of 45wt% extracts the red mud.

7. the method for claim 1, wherein concentration extract the red mud for the HCl of 18wt% to 45wt%.

8. the method for claim 1, wherein at a temperature of 160 DEG C to 190 DEG C concentration be 18wt% extremely The HCl of 45wt% extracts the red mud.

9. the method for claim 1, wherein at a temperature of 160 DEG C to 175 DEG C concentration be 18wt% extremely The HCl of 45wt% extracts the red mud.

10. the method for claim 1, wherein at a temperature of 185 DEG C to 190 DEG C concentration be 18wt% extremely The HCl of 45wt% extracts the red mud.

11. the method for claim 1, wherein at a temperature of 125 DEG C to 225 DEG C concentration be 18wt% extremely The HCl of 32wt% extracts the red mud.

12. the method for claim 1, wherein at a temperature of 160 DEG C to 190 DEG C concentration be 18wt% extremely The HCl of 32wt% extracts the red mud.

13. the method for claim 1, wherein at a temperature of 160 DEG C to 175 DEG C concentration be 18wt% extremely The HCl of 32wt% extracts the red mud.

14. the method for claim 1, wherein at a temperature of 185 DEG C to 190 DEG C concentration be 18wt% extremely The HCl of 32wt% extracts the red mud.

15. the method for claim 1, HCl of the concentration for 4M to 8M wherein at a temperature of 140 DEG C to 165 DEG C Extract the red mud.

16. the method for claim 1, wherein at 140 DEG C to 165 DEG C of temperature and the pressure of 60psig to 90psig Concentration extracts the red mud for the HCl of 6M.

17. methods as any one of claim 1 to 16, wherein methods described are also included by making produced gaseous state HCl is contacted with water and is carried out gaseous state HCl described in recirculation to obtain concentration as the compositionss of 25wt% to 45wt%, and by described group Compound is used for extracting the red mud.

18. methods as claimed in claim 17, the produced gaseous state HCl of wherein described recirculation contact dense to obtain with water The compositionss for 26wt% to 42wt% are spent, and makes the compositionss red with described at a temperature of 125 DEG C to 225 DEG C Mud reacts to extract the red mud.

19. methods as claimed in claim 17, the produced gaseous state HCl of wherein described recirculation contact dense to obtain with water The compositionss for 28wt% to 40wt% are spent, and makes the compositionss red with described at a temperature of 150 DEG C to 200 DEG C Mud reacts to extract the red mud.

20. methods as claimed in claim 17, the produced gaseous state HCl of wherein described recirculation contact dense to obtain with water The compositionss for 30wt% to 38wt% are spent, and makes the compositionss red with described at a temperature of 150 DEG C to 200 DEG C Mud reacts to extract the red mud.

21. methods as any one of claim 1 to 16, wherein methods described are also included by making produced gaseous state HCl is contacted with water and is carried out gaseous state HCl described in recirculation to obtain concentration as the compositionss of 18wt% to 36wt%.

22. methods as any one of claim 1 to 16, wherein methods described are also included by making produced gaseous state HCl is contacted with water and is carried out gaseous state HCl described in recirculation to obtain concentration as the compositionss of 25wt% to 36wt%.

23. methods as claimed in claim 20, wherein make the compositionss red with described at a temperature of 160 DEG C to 180 DEG C Mud reacts to extract the red mud.

24. methods as claimed in claim 20, wherein make the compositionss red with described at a temperature of 160 DEG C to 175 DEG C Mud reacts to extract the red mud.

25. methods as claimed in claim 20, wherein make the compositionss red with described at a temperature of 165 DEG C to 170 DEG C Mud reacts to extract the red mud.

26. methods as any one of claim 1 to 16,18 to 20 and 23 to 25, wherein described liquid is comprising extremely A kind of few iron chloride.

27. methods as claimed in claim 26, wherein described at least one iron chloride are FeCl₂、FeCl₃Or its mixture.

28. methods as claimed in claim 26, wherein described liquid are condensed at least one iron chloride concentration and are At least concentrated solution of 30wt%；Then hydrolyze at a temperature of 155 DEG C to 350 DEG C.

29. methods as claimed in claim 26, wherein described liquid are condensed at least one iron chloride concentration and are At least concentrated solution of 30wt%；Then at least one iron chloride is hydrolyzed at a temperature of 155 DEG C to 350 DEG C, while will Ferric chloride concn maintains at least level of 65wt%, to generate the compositionss of the bloodstone comprising liquid and precipitation, and returns Receive the bloodstone.

30. methods as claimed in claim 26, wherein hydrolyze at least one ferrum chlorine at a temperature of 165 DEG C to 170 DEG C Compound.

31. methods as claimed in claim 26, wherein described liquid are condensed at least one iron chloride concentration and are At least concentrated solution of 30wt%；Then at least one iron chloride is hydrolyzed at a temperature of 155 DEG C to 350 DEG C, while will Ferric chloride concn maintains at least level of 65wt%, to generate the compositionss of the bloodstone comprising liquid and precipitation；Reclaim institute State bloodstone；And from the liquids recovery rare metal.

32. methods as claimed in claim 31, wherein described rare metal are rare earth element.

33. methods as claimed in claim 31, wherein hydrolyze at least one ferrum chlorine at a temperature of 155 DEG C to 170 DEG C Compound.

34. methods as claimed in claim 31, after being additionally included in the recovery rare metal, make the liquid anti-with HCl Should be causing MgCl₂Precipitation, and reclaimed.

35. methods as claimed in claim 34, are also included MgCl₂It is sintered into MgO.

36. methods as claimed in claim 34, are also included MgCl₂MgO is sintered into, and by making produced gaseous state HCl Contact with water carry out gaseous state HCl described in recirculation concentration is obtained as the compositionss of 25wt% to 45wt%, and by the combination Thing is used for extracting the red mud.

37. methods as claimed in claim 34, are also included MgCl₂MgO is sintered into, and by making produced gaseous state HCl Contact with water carry out gaseous state HCl described in recirculation concentration is obtained as the compositionss of 18wt% to 45wt%, and by the combination Thing is used for extracting the red mud.

38. methods as any one of claim 31 to 37, are additionally included in the downstream of the rare metal recovery, from institute Liquids recovery NaCl is stated, the NaCl and H is made₂SO₄Reaction, and optionally precipitate Na₂SO₄.

39. methods as any one of claim 31 to 37, are additionally included in the downstream of the rare metal recovery, from institute Liquids recovery KCl is stated, the KCl and H is made₂SO₄Reaction, and optionally precipitate K₂SO₄.

40. methods as any one of claim 31 to 37, are additionally included in the downstream of the rare metal recovery, from institute Liquids recovery NaCl is stated, is electrolysed to generate NaOH and NaOCl.

41. methods as any one of claim 31 to 37, are additionally included in the downstream of the rare metal recovery, from institute Liquids recovery KCl is stated, the KCl reactions is made, is electrolysed to generate KOH and KOCl.

42. methods as claimed in claim 26, wherein described liquid are condensed at least one iron chloride concentration and are At least concentrated solution of 30wt%；Then at least one iron chloride is hydrolyzed at a temperature of 155 DEG C to 350 DEG C, while will Ferric chloride concn maintains at least level of 65wt%, to generate the compositionss of the bloodstone comprising liquid and precipitation；Reclaim institute State bloodstone；And from the liquid extraction NaCl and/or KCl.

43. methods as claimed in claim 42, also include making the NaCl and H₂SO₄React optionally to precipitate Na₂SO₄.

44. methods as claimed in claim 42, also include making the KCl and H₂SO₄React optionally to precipitate K₂SO₄.

45. methods as claimed in claim 42, also include the electrolysis for carrying out the NaCl, to generate NaOH and NaOCl.

46. methods as claimed in claim 42, also include the electrolysis for carrying out the KCl, to generate KOH and KOCl.

47. methods as any one of claim 1 to 16,18 to 20,23 to 25,27 to 37 and 42 to 46, wherein Methods described includes separating the solid with the lixiviating solution, and to wash the solid to obtain purity be at least 95% Silicon dioxide.

48. methods as any one of claim 1 to 16,18 to 20,23 to 25,27 to 37 and 42 to 46, wherein Methods described includes separating the solid with the lixiviating solution, and to wash the solid to obtain purity be at least 98% Silicon dioxide.

49. methods as any one of claim 1 to 16,18 to 20,23 to 25,27 to 37 and 42 to 46, wherein Methods described includes separating the solid with the lixiviating solution, and to wash the solid to obtain purity be at least 99% Silicon dioxide.

50. methods as any one of claim 1 to 16,18 to 20,23 to 25,27 to 37 and 42 to 46, wherein Methods described includes making the lixiviating solution react with gaseous state HCl to obtain the liquid and include the aluminum ions precipitation Thing, the precipitate pass through crystalline A lCl₃·6H₂O and formed.

51. methods as any one of claim 1 to 16,18 to 20,23 to 25,27 to 37 and 42 to 46, wherein Methods described includes making the lixiviating solution with the reaction that dries gaseous state HCl obtaining the liquid and comprising described aluminum ions described Precipitate, the precipitate pass through crystalline A lCl₃·6H₂O and formed.

52. methods as claimed in claim 50, wherein described gaseous state HCl have the HCl concentration of at least 85wt%.

53. methods as claimed in claim 50, wherein described gaseous state HCl have the HCl concentration of at least 90wt%.

54. methods as claimed in claim 50, wherein described gaseous state HCl have the HCl concentration of 90wt%.

55. methods as claimed in claim 50, wherein described gaseous state HCl have the concentration of 90wt% to 95wt%.

56. methods as claimed in claim 50, wherein in AlCl₃·6H₂In the crystallization process of O, the liquid is remained The HCl concentration of 25wt% to 35wt%.

57. methods as claimed in claim 50, wherein in AlCl₃·6H₂In the crystallization process of O, the liquid is remained The HCl concentration of 30wt% to 32wt%.

58. methods as claimed in claim 50, wherein described react the lixiviating solution and HCl the step of used in HCl is effectively by AlCl by described₃Change into Al₂O₃Under conditions of the step of heat the precipitate in produced by gaseous state HCl is obtained.

59. sides as any one of claim 1 to 16,18 to 20,23 to 25,27 to 37,42 to 46 and 52 to 58 Method, wherein methods described include the HCl reactions for making the lixiviating solution with reclaim in the process and concentration is at least 30%, To obtain the liquid and include the aluminum ions precipitate, the precipitate passes through crystalline A lCl₃·6H₂O and shape Into.

Method described in 60. claim 50, wherein described crystallization are carried out at a temperature of 45 DEG C to 65 DEG C.

Method described in 61. claim 50, wherein described crystallization are carried out at a temperature of 50 DEG C to 60 DEG C.

62. such as claim 1 to 16,18 to 20,23 to 25,27 to 37,42 to 46,52 to 58 and any one of 60 to 61 Described method, wherein methods described are included by calcining AlCl₃·6H₂O and by AlCl₃·6H₂O changes into Al₂O₃.

63. such as claim 1 to 16,18 to 20,23 to 25,27 to 37,42 to 46,52 to 58 and any one of 60 to 61 Described method, wherein methods described are included at a temperature of at least 1200 DEG C and heat the precipitate with by AlCl₃·6H₂O turns Chemical conversion Al₂O₃.

64. such as claim 1 to 16,18 to 20,23 to 25,27 to 37,42 to 46,52 to 58 and any one of 60 to 61 Described method, wherein methods described are included at a temperature of at least 1250 DEG C and heat the precipitate with by AlCl₃·6H₂O turns Chemical conversion Al₂O₃.

65. such as claim 1 to 16,18 to 20,23 to 25,27 to 37,42 to 46,52 to 58 and any one of 60 to 61 Described method, wherein methods described are included at a temperature of at least 900 DEG C and heat the precipitate with by AlCl₃·6H₂O turns Chemical conversion Al₂O₃.

66. such as claim 1 to 16,18 to 20,23 to 25,27 to 37,42 to 46,52 to 58 and any one of 60 to 61 Described method, wherein methods described are included AlCl₃·6H₂O changes into α-Al₂O₃.

67. such as claim 1 to 16,18 to 20,23 to 25,27 to 37,42 to 46,52 to 58 and any one of 60 to 61 Described method, wherein methods described are included at a temperature of at least 350 DEG C and heat the precipitate with by AlCl₃·6H₂O turns Chemical conversion Al₂O₃.

68. such as claim 1 to 16,18 to 20,23 to 25,27 to 37,42 to 46,52 to 58 and any one of 60 to 61 Described method, wherein methods described are included at a temperature of 350 DEG C to 500 DEG C and heat the precipitate with by AlCl₃·6H₂O Change into Al₂O₃.

69. such as claim 1 to 16,18 to 20,23 to 25,27 to 37,42 to 46,52 to 58 and any one of 60 to 61 Described method, wherein methods described are included at a temperature of 375 DEG C to 450 DEG C and heat the precipitate with by AlCl₃·6H₂O Change into Al₂O₃.

70. such as claim 1 to 16,18 to 20,23 to 25,27 to 37,42 to 46,52 to 58 and any one of 60 to 61 Described method, wherein methods described are included at a temperature of 375 DEG C to 425 DEG C and heat the precipitate with by AlCl₃·6H₂O Change into Al₂O₃.

71. such as claim 1 to 16,18 to 20,23 to 25,27 to 37,42 to 46,52 to 58 and any one of 60 to 61 Described method, wherein methods described are included at a temperature of 385 DEG C to 400 DEG C and heat the precipitate with by AlCl₃·6H₂O Change into Al₂O₃.

72. methods as described in claim 69, wherein methods described are included AlCl₃·6H₂O changes into β-Al₂O₃.

Any one of 73. claim 1 to 16,18 to 20,23 to 25,27 to 37,42 to 46,52 to 58,60 to 61 and 72 Described method, wherein by AlCl₃·6H₂O changes into Al₂O₃Including being calcined by two benches circulating fluid bed reactor.

Any one of 74. claim 1 to 16,18 to 20,23 to 25,27 to 37,42 to 46,52 to 58,60 to 61 and 72 Described method, wherein by AlCl₃·6H₂O changes into Al₂O₃Including the two benches recirculating fluidized bed by including pre-heating system Reactor is calcined.

75. methods as described in claim 74, wherein described pre-heating system include plasma torch.

76. methods as described in claim 75, wherein described plasma torch are effectively preheated and enter calcination reactor Air.

77. methods as described in claim 75, wherein described plasma torch effectively produce steam, and the steam is sprayed Inject calcination reactor.

78. methods as described in claim 75, wherein described plasma torch effectively produce steam, and the steam is used as Fluidizing agent in fluidized-bed reactor.

79. as claim 1 to 16,18 to 20,23 to 25,27 to 37,42 to 46,52 to 58,60 to 61,72 and 75 to Method any one of 78, wherein by AlCl₃·6H₂O changes into Al₂O₃Including carrying out one-step calcination.

80. as claim 1 to 16,18 to 20,23 to 25,27 to 37,42 to 46,52 to 58,60 to 61,72 and 75 to Method any one of 78, wherein methods described are included by AlCl₃·6H₂O is calcined and by AlCl₃·6H₂O Change into Al₂O₃, described calcining include steam injection.

81. methods as described in claim 80, wherein steam is with the pressure injection of 200psig to 700psig.

82. methods as described in claim 80, wherein steam is with the pressure injection of 300psig to 700psig.

83. methods as described in claim 80, wherein steam is with the pressure injection of 400psig to 700psig.

84. methods as described in claim 80, wherein steam is with the pressure injection of 550psig to 650psig.

85. methods as described in claim 80, wherein steam is with the pressure injection of 575psig to 625psig.

86. methods as described in claim 80, wherein steam is with the pressure injection of 590psig to 610psig.

87. methods as described in claim 80, wherein injection steam and plasma torch are used for being fluidized.

88. methods as described in claim 80, wherein with the pressure injection steam and plasma of 590psig to 610psig Body torch is used for causing fluidisation.

89. methods as described in claim 80, wherein described steam is overheated.

90. as claim 1 to 16,18 to 20,23 to 25,27 to 37,42 to 46,52 to 58,60 to 61,72,75 to 78, with And the method any one of 81 to 89, wherein methods described includes by AlCl₃·6H₂O is calcined and is incited somebody to action AlCl₃·6H₂O is converted into AlCl₃, described calcining be by combustion of fossil fuels, carbon monoxide, propane, natural gas, refinery gas, Coal, or chloridating gas and/or solvent are providing.

91. as claim 1 to 16,18 to 20,23 to 25,27 to 37,42 to 46,52 to 58,60 to 61,72,75 to 78, with And the method any one of 81 to 89, wherein methods described includes by AlCl₃·6H₂O is calcined and is incited somebody to action AlCl₃·6H₂The Al that O is changed into₂O₃, the calcining is that the gas by burning as smeltery's air inlet or decelerator waste gas is mixed Compound is provided.

92. as claim 1 to 16,18 to 20,23 to 25,27 to 37,42 to 46,52 to 58,60 to 61,72,75 to 78, with And the method any one of 81 to 89, wherein methods described includes by AlCl₃·6H₂O is calcined and is incited somebody to action AlCl₃·6H₂The Al that O is changed into₂O₃, the calcining is provided by admixture of gas of the burning comprising following components：

CH₄：0 to 1vol%；

C₂H₆：0 to 2vol%；

C₃H₈：0 to 2vol%；

C₄H₁₀：0 to 1vol%；

N₂：0 to 0.5vol%；

H₂：0.25vol% to 15.1vol%；

CO：70vol% to 82.5vol%；With

CO₂：1.0vol%3.5vol%.

There is no O in 93. methods as described in claim 92, wherein described mixture₂.

94. as claim 1 to 16,18 to 20,23 to 25,27 to 37,42 to 46,52 to 58,60 to 61,72,75 to 78, with And the method any one of 81 to 89, wherein methods described includes by AlCl₃·6H₂O is calcined and is incited somebody to action AlCl₃·6H₂O changes into Al₂O₃, the calcining is provided by electrical heating, gas heating, microwave heating.

95. as claim 1 to 16,18 to 20,23 to 25,27 to 37,42 to 46,52 to 58,60 to 61,72,75 to 78,81 To the method any one of 89 and 93, wherein by AlCl₃·6H₂O changes into Al₂O₃Including by fluidized-bed reactor Calcined.

96. methods as described in claim 95, wherein described fluidized-bed reactor include urging selected from the metal of metal chloride Agent.

97. methods as described in claim 95, wherein described fluidized-bed reactor include FeCl₃、FeCl₂Or its mixture.

98. methods as described in claim 95, wherein described fluidized-bed reactor include FeCl₃.

99. as claim 1 to 16,18 to 20,23 to 25,27 to 37,42 to 46,52 to 58,60 to 61,72,75 to 78,81 To the method any one of 89,93 and 96 to 98, wherein methods described is semicontinuous method.

100. as claim 1 to 16,18 to 20,23 to 25,27 to 37,42 to 46,52 to 58,60 to 61,72,75 to 78, Method any one of 81 to 89,93 and 96 to 98, wherein methods described are continuation methods.

101. as claim 1 to 16,18 to 20,23 to 25,27 to 37,42 to 46,52 to 58,60 to 61,72,75 to 78, Method any one of 81 to 89,93 and 96 to 98, wherein methods described effectively provide at least 93% Al₂O₃Return Yield.

102. as claim 1 to 16,18 to 20,23 to 25,27 to 37,42 to 46,52 to 58,60 to 61,72,75 to 78, Method any one of 81 to 89,93 and 96 to 98, wherein methods described effectively provide 90% to 95% Al₂O₃ The response rate.

103. as claim 1 to 16,18 to 20,23 to 25,27 to 37,42 to 46,52 to 58,60 to 61,72,75 to 78, Method any one of 81 to 89,93 and 96 to 98, wherein methods described effectively provide at least 98% Fe₂O₃Return Yield.

104. as claim 1 to 16,18 to 20,23 to 25,27 to 37,42 to 46,52 to 58,60 to 61,72,75 to 78, Method any one of 81 to 89,93 and 96 to 98, wherein methods described effectively provide 98% to 99.5% Fe₂O₃The response rate.

105. as claim 1 to 16,18 to 20,23 to 25,27 to 37,42 to 46,52 to 58,60 to 61,72,75 to 78, Method any one of 81 to 89,93 and 96 to 98, wherein methods described effectively provide at least 96% MgO and return Yield.

106. as claim 1 to 16,18 to 20,23 to 25,27 to 37,42 to 46,52 to 58,60 to 61,72,75 to 78, Method any one of 81 to 89,93 and 96 to 98, wherein methods described effectively provide 96% to 98% MgO The response rate.

107. as claim 1 to 16,18 to 20,23 to 25,27 to 37,42 to 46,52 to 58,60 to 61,72,75 to 78, Method any one of 81 to 89,93 and 96 to 98, wherein methods described effectively provide at least 98% HCl and return Yield.

108. as claim 1 to 16,18 to 20,23 to 25,27 to 37,42 to 46,52 to 58,60 to 61,72,75 to 78, Method any one of 81 to 89,93 and 96 to 98, wherein methods described effectively provide at least 99% HCl and return Yield.

109. as claim 1 to 16,18 to 20,23 to 25,27 to 37,42 to 46,52 to 58,60 to 61,72,75 to 78, Method any one of 81 to 89,93 and 96 to 98, wherein methods described effectively provide 98% to 99.9% The HCl response rate.

110. as claim 1 to 16,18 to 20,23 to 25,27 to 37,42 to 46,52 to 58,60 to 61,72,75 to 78, Method any one of 81 to 89,93 and 96 to 98, wherein extracts under the pressure of 4barg to 10barg described red Mud.

111. as claim 1 to 16,18 to 20,23 to 25,27 to 37,42 to 46,52 to 58,60 to 61,72,75 to 78, Method any one of 81 to 89,93 and 96 to 98, wherein extracts under the pressure of 4barg to 8barg described red Mud.

112. as claim 1 to 16,18 to 20,23 to 25,27 to 37,42 to 46,52 to 58,60 to 61,72,75 to 78, Method any one of 81 to 89,93 and 96 to 98, wherein extracts under the pressure of 5barg to 6barg described red Mud.

113. as claim 1 to 16,18 to 20,23 to 25,27 to 37,42 to 46,52 to 58,60 to 61,72,75 to 78, Method any one of 81 to 89,93 and 96 to 98, before being additionally included in the extraction red mud, pre- extraction removes institute State the fluorine optionally included in red mud.

114. as claim 1 to 16,18 to 20,23 to 25,27 to 37,42 to 46,52 to 58,60 to 61,72,75 to 78, Method any one of 81 to 89,93 and 96 to 98, including extracting the red mud to obtain comprising aluminium ion with HCl The lixiviating solution and the solid, the solid is separated with the lixiviating solution；And further process the solid to incite somebody to action The Si for wherein including is separated with Ti.

115. as claim 1 to 16,18 to 20,23 to 25,27 to 37,42 to 46,52 to 58,60 to 61,72,75 to 78, Method any one of 81 to 89,93 and 96 to 98, including extracting the red mud to obtain comprising aluminium ion with HCl The lixiviating solution and the solid, the solid is separated with the lixiviating solution；And further with the HCl process solid So that the Si for wherein including is separated with Ti.

116. as claim 1 to 16,18 to 20,23 to 25,27 to 37,42 to 46,52 to 58,60 to 61,72,75 to 78, Method any one of 81 to 89,93 and 96 to 98, including extracting the red mud to obtain comprising aluminium ion with HCl The lixiviating solution and the solid, the solid is separated with the lixiviating solution；And in the presence of muriatic further The solid is processed with HCl to separate the Si for wherein including with Ti.

117. as claim 1 to 16,18 to 20,23 to 25,27 to 37,42 to 46,52 to 58,60 to 61,72,75 to 78, Method any one of 81 to 89,93 and 96 to 98, including extracting the red mud to obtain comprising aluminium ion with HCl The lixiviating solution and the solid, the solid is separated with the lixiviating solution；And at a temperature of less than 85 DEG C, in chlorine In the presence of compound, further the HCl with concentration less than 20wt% processes the solid to separate the Si for wherein including with Ti.

118. methods as described in claim 116, wherein with HCl and described in the chloride treatment, solid is obtaining comprising Ti Liquid portion and the solid portion comprising Si, and wherein the liquid portion is separated with the solid portion.

119. methods as described in claim 118, wherein with solid described in HCl and chloride treatment obtaining comprising TiCl₄'s Liquid portion.

120. methods as described in claim 119, wherein methods described are also included TiCl₄It is converted into TiO₂.

121. methods as described in claim 120, wherein by the 3rd liquid distillate of solvent extraction and subsequently from the solvent Extraction forms Titanium Dioxide, so as to by TiCl₄It is converted into TiO₂.

122. methods as described in claim 120, wherein TiCl₄With water and/or alkali reaction, to cause TiO₂Precipitation.

123. methods as described in claim 120, wherein pass through pyrohydrolysises by TiCl₄Change into TiO₂, thus produce HCl.

124. methods as described in claim 120, wherein pass through pyrohydrolysises by TiCl₄Change into TiO₂, thus produce and follow again The HCl of ring.

125. methods as described in claim 116, wherein described chloride is MgCl₂.

126. methods as described in claim 114, wherein described solid bag contain TiO₂And SiO₂And use Cl₂Institute is processed with carbon Solid is stated to obtain liquid portion and solid portion, and wherein makes the solid portion and the liquid portion separated from one another.

127. methods as described in claim 126, wherein described liquid portion include TiCl₂And/or TiCl₄.

128. methods as described in claim 126, wherein described liquid portion include TiCl₄.

129. methods as described in claim 128, also include heating TiCl₄To convert it into TiO₂.

130. methods as described in claim 116, the TiO for wherein being obtained by plasma torch purification₂.

131. as claim 1 to 16,18 to 20,23 to 25,27 to 37,42 to 46,52 to 58,60 to 61,72,75 to 78, Method any one of 81 to 89,93,96 to 98 and 118 to 130, wherein by the HCl purification for reclaiming and/or concentration.

The HCl for reclaiming wherein is passed through Membrane Materials process purification by 132. methods as described in claim 131.

133. methods as described in claim 131, the HCl for wherein reclaiming is gaseous state HCl, and uses H₂SO₄Process, so as to drop The low water yield present in the gaseous state HCl.

134. methods as described in claim 133, the HCl for wherein reclaiming is gaseous state HCl, and by packed column with H₂SO₄Inverse Stream contact, so that reduce the water yield present in the gaseous state HCl.

135. methods as described in claim 134, wherein described post is filled with polypropylene or PTT.

136. methods as described in claim 131, the concentration increase at least 50% of wherein described gaseous state HCl.

137. methods as described in claim 131, the concentration increase at least 60% of wherein described gaseous state HCl.

138. methods as described in claim 131, the concentration increase at least 70% of wherein described gaseous state HCl.

139. methods as described in claim 131, the HCl for wherein reclaiming is gaseous state HCl, and uses CaCl₂Process, so as to drop The low water yield present in the gaseous state HCl.

140. methods as described in claim 139, the HCl for wherein reclaiming are gaseous state HCl, and by being filled with CaCl₂'s Post, so that reduce the water yield present in the gaseous state HCl.

Method described in 141. claim 131, the wherein concentration of gaseous state HCl are increased to from the value less than azeotropic point of before processing The value higher than azeotropic point after process.

142. are used for the method for preparing aluminum, and methods described includes：

With HCl extraction red muds to obtain comprising aluminum ions lixiviating solution and solid at a temperature of 125 DEG C to 225 DEG C, and will The solid is separated with the lixiviating solution；

Make the lixiviating solution react with HCl to obtain the liquid comprising iron ion and include AlCl₃The described aluminum ions of form is sunk Starch, and the precipitate is separated with the liquid；

Effectively by AlCl₃Change into Al₂O₃Under conditions of heat the precipitate, and the gaseous state produced by optionally reclaiming HCl；And

By the Al₂O₃It is converted into aluminum.

143. methods as described in claim 142, wherein concentration are described red for the HCl extractions of 25wt% to 45wt% Mud.

144. methods as described in claim 142, wherein under the pressure of 50psig to 150psig, concentration is 25wt% HCl to 45wt% extracts the red mud.

145. methods as described in claim 142, wherein at a temperature of 160 DEG C to 190 DEG C concentration be 25wt% extremely The HCl of 45wt% extracts the red mud.

146. methods as described in claim 142, wherein at a temperature of 160 DEG C to 175 DEG C concentration be 25wt% extremely The HCl of 45wt% extracts the red mud.

147. methods as described in claim 142, wherein at a temperature of 185 DEG C to 190 DEG C concentration be 25wt% extremely The HCl of 45wt% extracts the red mud.

148. methods as described in claim 142, wherein at a temperature of 140 DEG C to 165 DEG C, concentration is 4M's to 8M HCl extracts the red mud.

149. methods as described in claim 142, wherein in 140 DEG C to 165 DEG C of temperature and the pressure of 60psig to 90psig Under power, concentration extracts the red mud for the HCl of 6M.

150. methods as described in claim 142, wherein concentration are described red for the HCl extractions of 18wt% to 45wt% Mud.

151. methods as described in claim 142, wherein at a temperature of 160 DEG C to 190 DEG C concentration be 18wt% extremely The HCl of 45wt% extracts the red mud.

152. methods as described in claim 142, wherein at a temperature of 160 DEG C to 175 DEG C concentration be 18wt% extremely The HCl of 45wt% extracts the red mud.

153. methods as described in claim 142, wherein at a temperature of 185 DEG C to 190 DEG C concentration be 18wt% extremely The HCl of 45wt% extracts the red mud.

154. methods as described in claim 142, wherein at a temperature of 125 DEG C to 225 DEG C concentration be 18wt% extremely The HCl of 32wt% extracts the red mud.

155. methods as described in claim 142, wherein at a temperature of 160 DEG C to 190 DEG C concentration be 18wt% extremely The HCl of 32wt% extracts the red mud.

156. methods as described in claim 142, wherein at a temperature of 160 DEG C to 175 DEG C concentration be 18wt% extremely The HCl of 32wt% extracts the red mud.

157. methods as described in claim 142, wherein at a temperature of 185 DEG C to 190 DEG C concentration be 18wt% extremely The HCl of 32wt% extracts the red mud.

158. methods as any one of claim 142 to 157, wherein methods described are also included by making described being produced Raw gaseous state HCl is contacted with water and is carried out gaseous state HCl described in recirculation to obtain concentration as the compositionss of 25wt% to 45wt%, and It is used for extracting the red mud by the compositionss.

159. methods as described in claim 158, the produced gaseous state HCl of wherein described recirculation contact to obtain with water The compositionss of the concentration for 26wt% to 42wt%, and make the compositionss at a temperature of 125 DEG C to 225 DEG C with described Red mud reacts to extract the red mud.

160. methods as described in claim 158, the produced gaseous state HCl of wherein described recirculation contact to obtain with water The compositionss of the concentration for 28wt% to 40wt%, and make the compositionss at a temperature of 150 DEG C to 200 DEG C with described Red mud reacts to extract the red mud.

161. methods as described in claim 158, the produced gaseous state HCl of wherein described recirculation contact to obtain with water The compositionss of the concentration for 30wt% to 38wt%, and make the compositionss at a temperature of 150 DEG C to 200 DEG C with described Red mud reacts to extract the red mud.

162. methods as described in claim 161, the produced gaseous state HCl of wherein described recirculation contact to obtain with water The compositionss of the concentration for 18wt% to 36wt%.

163. methods as described in claim 161, the produced gaseous state HCl of wherein described recirculation contact to obtain with water The compositionss of the concentration for 25wt% to 36wt%.

164. methods as described in claim 161, wherein make the compositionss at a temperature of 160 DEG C to 180 DEG C with described Red mud reacts to extract the red mud.

165. methods as described in claim 161, wherein make the compositionss at a temperature of 160 DEG C to 175 DEG C with described Red mud reacts to extract the red mud.

166. methods as described in claim 161, wherein make the compositionss at a temperature of 165 DEG C to 170 DEG C with described Red mud reacts to extract the red mud.

167. methods as any one of claim 142 to 157 and 159 to 166, wherein described liquid is comprising extremely A kind of few iron chloride.

168. methods as described in claim 167, wherein described at least one iron chloride are FeCl₂、FeCl₃Or which mixes Thing.

169. methods as described in claim 167, wherein described liquid are condensed at least one iron chloride concentration It is at least concentrated solution of 30wt%；Then hydrolyze at a temperature of 155 DEG C to 350 DEG C.

170. methods as described in claim 167, wherein described liquid are condensed at least one iron chloride concentration It is at least concentrated solution of 30wt%；Then at least one iron chloride is hydrolyzed at a temperature of 155 DEG C to 350 DEG C, while Ferric chloride concn is maintained at least level of 65wt%, to generate the compositionss of the bloodstone comprising liquid and precipitation, and Reclaim the bloodstone.

171. methods as described in claim 167, wherein hydrolyze at least one ferrum at a temperature of 165 DEG C to 170 DEG C Chloride.

172. methods as described in claim 167, wherein described liquid are condensed at least one iron chloride concentration It is at least concentrated solution of 30wt%；Then at least one iron chloride is hydrolyzed at a temperature of 155 DEG C to 350 DEG C, while Ferric chloride concn is maintained at least level of 65wt%, to generate the compositionss of the bloodstone comprising liquid and precipitation；Reclaim The bloodstone；And from the liquids recovery rare metal.

173. methods as described in claim 172, wherein described rare metal are rare earth element.

174. methods as described in claim 172, wherein hydrolyze at least one ferrum at a temperature of 155 DEG C to 170 DEG C Chloride.

175. methods as described in claim 172 to 174, after being additionally included in the recovery rare metal, make the liquid with HCl reacts to cause MgCl₂Precipitation, and reclaimed.

176. methods as described in claim 174, are also included MgCl₂It is sintered into MgO.

177. methods as described in claim 175, are also included MgCl₂MgO is sintered into, and by making produced gaseous state HCl is contacted with water and is carried out gaseous state HCl described in recirculation to obtain concentration as the compositionss of 25wt% to 45wt%, and by described group Compound is used for extracting the red mud.

178. methods as described in claim 175, are also included MgCl₂MgO is sintered into, and by making produced gaseous state HCl is contacted with water and is carried out gaseous state HCl described in recirculation to obtain concentration as the compositionss of 18wt% to 45wt%, and by described group Compound is used for extracting the red mud.

179. methods as any one of claim 172 to 174 and 176 to 178, are additionally included in rare metal and return The downstream of receipts, from liquids recovery NaCl, makes the NaCl and H₂SO₄Reaction, and optionally precipitate Na₂SO₄.

180. methods as any one of claim 172 to 174 and 176 to 178, are additionally included in rare metal and return The downstream of receipts, from liquids recovery KCl, makes the KCl and H₂SO₄Reaction, and optionally precipitate K₂SO₄.

181. methods as any one of claim 172 to 174 and 176 to 178, are additionally included in rare metal and return The downstream of receipts, from liquids recovery NaCl, is electrolysed to generate NaOH and NaOCl.

182. methods as any one of claim 172 to 174 and 176 to 178, are additionally included in rare metal and return The downstream of receipts, from liquids recovery KCl, makes the KCl reactions, is electrolysed to generate KOH and KOCl.

183. methods as described in claim 167, wherein described liquid are condensed at least one iron chloride concentration It is at least concentrated solution of 30wt%；Then at least one iron chloride is hydrolyzed at a temperature of 155 DEG C to 350 DEG C, while Ferric chloride concn is maintained at least level of 65wt%, to generate the compositionss of the bloodstone comprising liquid and precipitation；Reclaim The bloodstone；And from the liquid extraction NaCl and/or KCl.

184. methods as described in claim 183, also include making the NaCl and H₂SO₄React optionally to precipitate Na₂SO₄.

185. methods as described in claim 183, also include making the KCl and H₂SO₄React optionally to precipitate K₂SO₄.

186. methods as described in claim 183, also include the electrolysis for carrying out the NaCl, to generate NaOH and NaOCl.

187. methods as described in claim 182, also include the electrolysis for carrying out the KCl, to generate KOH and KOCl.

188. methods as any one of claim 142 to 157 and 159 to 166, wherein methods described include by The solid is separated with the lixiviating solution and washs the solid, so as to obtain the silicon dioxide that purity is at least 95%.

189. methods as any one of claim 142 to 157 and 159 to 166, wherein methods described include by The solid is separated with the lixiviating solution and washs the solid, so as to obtain the silicon dioxide that purity is at least 98%.

190. methods as any one of claim 142 to 157 and 159 to 166, wherein methods described include by The solid is separated with the lixiviating solution and washs the solid, so as to obtain the silicon dioxide that purity is at least 99%.

191. methods as any one of claim 142 to 157 and 159 to 166, wherein methods described include making The lixiviating solution reacts to obtain the liquid and include the aluminum ions precipitate, the precipitate with gaseous state HCl By crystalline A lCl₃·6H₂O and formed.

192. methods as any one of claim 142 to 157 and 159 to 166, wherein methods described include making The lixiviating solution is reacted with gaseous state HCl is dried to obtain the liquid and include the aluminum ions precipitate, described heavy Starch passes through crystalline A lCl₃·6H₂O and formed.

193. methods as described in claim 191, wherein described gaseous state HCl have the HCl concentration of at least 85wt%.

194. methods as described in claim 191, wherein described gaseous state HCl have the HCl concentration of at least 90wt%.

195. methods as described in claim 191, wherein described gaseous state HCl have the HCl concentration of 90wt%.

196. methods as described in claim 191, wherein described gaseous state HCl have the concentration of 90wt% to 95wt%.

197. methods as described in claim 191, wherein in AlCl₃·6H₂In the crystallization process of O, the liquid keeps HCl concentration for 25wt% to 35wt%.

198. methods as described in claim 191, wherein in AlCl₃·6H₂In the crystallization process of O, the liquid keeps HCl concentration for 30wt% to 32wt%.

199. methods as described in claim 191, wherein described react the lixiviating solution and HCl the step of used in HCl is effectively by AlCl by described₃Change into Al₂O₃Under conditions of the step of heat the precipitate in produced by gaseous state HCl is obtained.

200. methods as any one of claim 142 to 157 and 159 to 166, wherein methods described include making The lixiviating solution and the HCl reactions that reclaim in the process and concentration is at least 30%, to obtain the liquid and include The aluminum ions precipitate, the precipitate pass through crystalline A lCl₃·6H₂O and formed.

Method described in 201. claim 191, wherein described crystallization are carried out at a temperature of 45 DEG C to 65 DEG C.

Method described in 202. claim 191, wherein described crystallization are carried out at a temperature of 50 DEG C to 60 DEG C.

203. methods as any one of claim 142 to 157 and 159 to 166, wherein methods described include leading to Cross to AlCl₃·6H₂O is calcined and by AlCl₃·6H₂O changes into Al₂O₃.

204. methods as any one of claim 142 to 157 and 159 to 166, wherein methods described are included in The precipitate is heated at a temperature of at least 1200 DEG C with by AlCl₃·6H₂O changes into Al₂O₃.

205. methods as any one of claim 142 to 157 and 159 to 166, wherein methods described are included in The precipitate is heated at a temperature of at least 1250 DEG C with by AlCl₃·6H₂O changes into Al₂O₃.

206. methods as any one of claim 142 to 157 and 159 to 166, wherein methods described are included in The precipitate is heated at a temperature of at least 900 DEG C with by AlCl₃·6H₂O changes into Al₂O₃.

207. methods as any one of claim 142 to 157 and 159 to 166, wherein methods described include by AlCl₃·6H₂O changes into α-Al₂O₃.

208. methods as any one of claim 142 to 157 and 159 to 166, wherein methods described are included in The precipitate is heated at a temperature of at least 350 DEG C with by AlCl₃·6H₂O changes into Al₂O₃.

209. methods as any one of claim 142 to 157 and 159 to 166, wherein methods described are included in The precipitate is heated at a temperature of 350 DEG C to 500 DEG C with by AlCl₃·6H₂O changes into Al₂O₃.

210. methods as described in claim 189, wherein methods described are included in heating institute at a temperature of 375 DEG C to 450 DEG C Precipitate is stated with by AlCl₃·6H₂O changes into Al₂O₃.

211. methods as any one of claim 142 to 157 and 159 to 166, wherein methods described are included in The precipitate is heated at a temperature of 375 DEG C to 425 DEG C with by AlCl₃·6H₂O changes into Al₂O₃.

212. methods as described in claim 189, wherein methods described are included in heating institute at a temperature of 385 DEG C to 400 DEG C Precipitate is stated with by AlCl₃·6H₂O changes into Al₂O₃.

213. methods as described in claim 208, wherein methods described are included AlCl₃·6H₂O changes into β-Al₂O₃.

Method any one of 214. claim 142 to 157 and 159 to 166, wherein by AlCl₃·6H₂O is converted Into Al₂O₃Including being calcined by two benches circulating fluid bed reactor.

Method any one of 215. claim 142 to 157 and 159 to 166, wherein by AlCl₃·6H₂O is converted Into Al₂O₃Including by including that the two benches circulating fluid bed reactor of pre-heating system is calcined.

216. methods as described in claim 215, wherein described pre-heating system include plasma torch.

217. methods as described in claim 215, wherein described plasma torch effectively preheat entrance calcination reactor Air.

218. methods as described in claim 215, wherein described plasma torch effectively produce steam, the steam quilt Spurt into calcination reactor.

219. methods as described in claim 215, wherein described plasma torch effectively produce steam, and the steam is made Fluidizing agent in for fluidized-bed reactor.

220. methods as any one of claim 142 to 157 and 159 to 166, wherein by AlCl₃·6H₂O turns Chemical conversion Al₂O₃Including carrying out one-step calcination.

221. methods as any one of claim 142 to 157 and 159 to 166, wherein methods described include leading to Cross to AlCl₃·6H₂O is calcined and by AlCl₃·6H₂O changes into Al₂O₃, described calcining include steam injection.

222. methods as described in claim 221, wherein steam is with the pressure injection of 200psig to 700psig.

223. methods as described in claim 221, wherein steam is with the pressure injection of 300psig to 700psig.

224. methods as described in claim 221, wherein steam is with the pressure injection of 400psig to 700psig.

225. methods as described in claim 221, wherein steam is with the pressure injection of 550psig to 650psig.

226. methods as described in claim 221, wherein steam is with the pressure injection of 575psig to 625psig.

227. methods as described in claim 221, wherein steam is with the pressure injection of 590psig to 610psig.

228. methods as described in claim 221, wherein injection steam and plasma torch are used for causing fluidisation.

229. methods as described in claim 221, wherein described steam is overheated.

230. methods as any one of claim 142 to 157 and 159 to 166, wherein methods described include leading to Cross to AlCl₃·6H₂O is calcined and by AlCl₃·6H₂O is converted into AlCl₃, described calcining be by combustion of fossil fuels, one Carbonoxide, propane, natural gas, refinery gas, coal, or chloridating gas and/or solvent are providing.

231. methods as any one of claim 142 to 157 and 159 to 166, wherein methods described include leading to Cross to AlCl₃·6H₂O is calcined and by AlCl₃·6H₂The Al that O is changed into₂O₃, the calcining is to be used as smelting by burning The admixture of gas of factory's air inlet or decelerator waste gas is provided.

232. methods as any one of claim 142 to 157 and 159 to 166, wherein methods described include leading to Cross to AlCl₃·6H₂O is calcined and by AlCl₃·6H₂The Al that O is changed into₂O₃, the calcining is comprising following by burning The admixture of gas of component is provided：

CH₄：0 to 1vol%；

C₂H₆：0 to 2vol%；

C₃H₈：0 to 2vol%；

C₄H₁₀：0 to 1vol%；

N₂：0 to 0.5vol%；

H₂：0.25vol% to 15.1vol%；

CO：70vol% to 82.5vol%；With

CO₂：1.0vol%3.5vol%.

There is no O in 233. methods as described in claim 232, wherein described mixture₂.

234. methods as any one of claim 142 to 157 and 159 to 166, wherein methods described include leading to Cross to AlCl₃·6H₂O is calcined and by AlCl₃·6H₂O changes into Al₂O₃, the calcining is added by electrical heating, gas Heat, microwave heating are provided.

235. methods as any one of claim 142 to 157 and 159 to 166, wherein by AlCl₃·6H₂O turns Chemical conversion Al₂O₃Including being calcined by fluidized-bed reactor.

236. methods as described in claim 235, wherein described fluidized-bed reactor include the metal selected from metal chloride Catalyst.

237. methods as described in claim 235, wherein described fluidized-bed reactor include FeCl₃、FeCl₂Or its mixture.

238. methods as described in claim 235, wherein described fluidized-bed reactor include FeCl₃.

239. methods as any one of claim 142 to 157 and 159 to 166, wherein methods described are partly to connect Continuous method.

240. methods as any one of claim 142 to 157 and 159 to 166, wherein methods described are continuous Method.

241. methods as any one of claim 142 to 157 and 159 to 166, wherein methods described are effectively At least 93% Al is provided₂O₃The response rate.

242. methods as any one of claim 142 to 157 and 159 to 166, wherein methods described are effectively 90% to 95% Al is provided₂O₃The response rate.

243. methods as any one of claim 142 to 157 and 159 to 166, wherein methods described are effectively At least 98% Fe is provided₂O₃The response rate.

244. methods as any one of claim 142 to 157 and 159 to 166, wherein methods described are effectively 98% to 99.5% Fe is provided₂O₃The response rate.

245. methods as any one of claim 142 to 157 and 159 to 166, wherein methods described are effectively At least 96% MgO response rate is provided.

246. methods as any one of claim 142 to 157 and 159 to 166, wherein methods described are effectively 96% to the 98% MgO response rate is provided.

247. methods as any one of claim 142 to 157 and 159 to 166, wherein methods described are effectively At least 98% HCl response rate is provided.

248. methods as any one of claim 142 to 157 and 159 to 166, wherein methods described are effectively At least 99% HCl response rate is provided.

249. methods as any one of claim 142 to 157 and 159 to 166, wherein methods described are effectively 98% to the 99.9% HCl response rate is provided.

250. methods as any one of claim 142 to 157 and 159 to 166, wherein in 4barg to 10barg Pressure under extract the red mud.

251. methods as any one of claim 142 to 157 and 159 to 166, wherein in 4barg to 8barg Pressure under extract the red mud.

252. methods as any one of claim 142 to 157 and 159 to 166, wherein in 5barg to 6barg Pressure under extract the red mud.

253. methods as any one of claim 142 to 157 and 159 to 166, are additionally included in extraction described red Before mud, pre- extraction removes the fluorine optionally included in the red mud.

254. methods as any one of claim 142 to 157 and 159 to 166, described red including being extracted with HCl The solid is separated with the lixiviating solution by mud with obtaining comprising the aluminum ions lixiviating solution and the solid；And enter one Step processes the solid to separate the Si for wherein including with Ti.

255. methods as any one of claim 142 to 157 and 159 to 166, described red including being extracted with HCl The solid is separated with the lixiviating solution by mud with obtaining comprising the aluminum ions lixiviating solution and the solid；And enter one Step processes the solid with HCl to separate the Si for wherein including with Ti.

256. methods as any one of claim 142 to 157 and 159 to 166, described red including being extracted with HCl The solid is separated with the lixiviating solution by mud with obtaining comprising the aluminum ions lixiviating solution and the solid；And in chlorine Further process the solid with HCl in the presence of compound to separate the Si for wherein including with Ti.

257. methods as any one of claim 142 to 157 and 159 to 166, described red including being extracted with HCl The solid is separated with the lixiviating solution by mud with obtaining comprising the aluminum ions lixiviating solution and the solid；And low At a temperature of 85 DEG C, in the presence of muriatic, further with concentration less than 20wt% HCl process the solid with by its In the Si that includes separate with Ti.

258. methods as described in claim 255, wherein with HCl and described in the chloride treatment, solid is obtaining comprising Ti Liquid portion and the solid portion comprising Si, and wherein the liquid portion is separated with the solid portion.

259. methods as described in claim 258, wherein with solid described in HCl and chloride treatment obtaining comprising TiCl₄'s Liquid portion.

260. methods as described in claim 259, methods described are also included TiCl₄It is converted into TiO₂.

261. methods as described in claim 260, wherein by the 3rd liquid distillate of solvent extraction and subsequently from the solvent Extraction forms Titanium Dioxide, so as to by TiCl₄It is converted into TiO₂.

262. methods as described in claim 260, wherein TiCl₄With water and/or alkali reaction, to cause TiO₂Precipitation.

263. methods as described in claim 260, wherein pass through pyrohydrolysises by TiCl₄Change into TiO₂, thus produce HCl.

264. methods as described in claim 260, wherein pass through pyrohydrolysises by TiCl₄Change into TiO₂, thus produce and follow again The HCl of ring.

265. methods as described in claim 256, wherein described chloride is MgCl₂.

266. methods as described in claim 254, wherein described solid bag contain TiO₂And SiO₂And use Cl₂Institute is processed with carbon Solid is stated to obtain liquid portion and solid portion, and wherein makes the solid portion and the liquid portion separated from one another.

267. methods as described in claim 266, wherein described liquid portion include TiCl₂And/or TiCl₄.

268. methods as described in claim 266, wherein described liquid portion include TiCl₄.

269. methods as described in claim 267, also include heating TiCl₄To convert it into TiO₂.

270. methods as described in claim 256, the TiO for wherein being obtained by plasma torch purification₂.

271. methods as any one of claim 142 to 157 and 159 to 166, the HCl purification that will wherein reclaim And/or concentration.

The HCl for reclaiming wherein is passed through Membrane Materials process purification by 272. methods as described in claim 271.

273. methods as described in claim 271, the HCl for wherein reclaiming is gaseous state HCl, and uses H₂SO₄Process, so as to drop The low water yield present in the gaseous state HCl.

274. methods as described in claim 273, the HCl for wherein reclaiming is gaseous state HCl, and by packed column with H₂SO₄Inverse Stream contact, so that reduce the water yield present in the gaseous state HCl.

275. methods as described in claim 274, wherein described post is filled with polypropylene or PTT.

276. methods as described in claim 271, the concentration increase at least 50% of wherein described gaseous state HCl.

277. methods as described in claim 271, the concentration increase at least 60% of wherein described gaseous state HCl.

278. methods as described in claim 271, the concentration increase at least 70% of wherein described gaseous state HCl.

279. methods as described in claim 271, the HCl for wherein reclaiming is gaseous state HCl, and uses CaCl₂Process, so as to drop The low water yield present in the gaseous state HCl.

280. methods as described in claim 271, the HCl for wherein reclaiming are gaseous state HCl, and by being filled with CaCl₂'s Post, so that reduce the water yield present in the gaseous state HCl.

Method described in 281. claim 271, the wherein concentration of gaseous state HCl are increased to from the value less than azeotropic point of before processing The value higher than azeotropic point after process.

Method any one of 282. claim 142 to 157 and 159 to 166, wherein Al₂O₃Turn to described in aluminum Change is carried out by Hall-H é roult methods.

Method any one of 283. claim 142 to 157 and 159 to 166, wherein Al₂O₃Turn to described in aluminum Change is carried out at a temperature of less than 200 DEG C by using reducing environment and carbon.

Method any one of 284. claim 142 to 157 and 159 to 166, wherein Al₂O₃Turn to described in aluminum Change is carried out by Wohler methods.

Method any one of 285. claim 142 to 157 and 159 to 166, wherein Al₂O₃Turn to described in aluminum Change is by by Al₂O₃It is converted into Al₂S₃And subsequently by Al₂S₃It is converted into what aluminum was carried out.

286. are used for the method that processes red mud, and methods described includes：

At a temperature of 125 DEG C to 225 DEG C extract the red mud comprising the first metal to obtain comprising first gold medal with HCl The lixiviating solution and solid of the ion of category, and the solid is separated with the lixiviating solution；

The lixiviating solution is made to react the muriatic precipitate to obtain liquid and comprising the first metal with HCl, and will be described Precipitate is separated with the liquid；And

It is described heavy to heat under conditions of the oxide that the chloride of first metal is effectively changed into first metal Starch.

287. methods as described in claim 286, wherein described liquid include the second metal.

288. methods as described in claim 287, wherein described second metal selected from aluminum, ferrum, zinc, copper, gold, silver, molybdenum, cobalt, Magnesium, lithium, manganese, nickel, palladium, platinum, thorium, phosphorus, uranium, titanium and its mixture and/or at least one rare earth element.

289. methods as described in claim 287, wherein described second metal is selected from least one rare metal.

290. methods as described in claim 287, wherein described second metal is ferrum.

291. methods as any one of claim 287 to 290, wherein methods described include by described precipitation with described Liquid is separated, and heats second metal bimetallic chloride is converted into the bimetallic oxidation Thing.

292. methods as any one of claim 287 to 290, wherein methods described include：

The solid is separated with the lixiviating solution；

The solid is carried with acidleach to obtain another lixiviating solution；And

The 3rd metal is reclaimed from another lixiviating solution.

293. methods as described in claim 292, wherein described 3rd metal selected from aluminum, ferrum, zinc, copper, gold, silver, molybdenum, cobalt, Magnesium, lithium, manganese, nickel, palladium, platinum, thorium, phosphorus, uranium and titanium and/or at least one rare earth element.

294. methods as described in claim 292, wherein described 3rd metal is selected from least one rare metal.

295. methods as described in claim 292, wherein described 3rd metal is titanium.

296. methods as any one of claim 286 to 290 and 293 to 295, wherein described first metal choosing From aluminum, ferrum, zinc, copper, gold, silver, molybdenum, cobalt, magnesium, lithium, manganese, nickel, palladium, platinum, thorium, phosphorus, uranium and titanium and/or at least one rare earth unit Element.

297. methods as any one of claim 286 to 290 and 293 to 295, wherein described first metal choosing From at least one rare metal.